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.

Ternary iron(II) complex with an emissive imidazopyridine arm from Schiff base cyclizations and its oxidative DNA cleavage activity.

Science.gov (United States)

Mukherjee, Arindam; Dhar, Shanta; Nethaji, Munirathinam; Chakravarty, Akhil R

2005-01-21

The ternary iron(II) complex [Fe(L')(L")](PF6)3(1) as a synthetic model for the bleomycins, where L' and L" are formed from metal-mediated cyclizations of N,N'-(2-hydroxypropane-1,3-diyl)bis(pyridine-2-aldimine)(L), is synthesized and structurally characterized by X-ray crystallography. In the six-coordinate iron(ii) complex, ligands L' and L" show tetradentate and bidentate chelating modes of bonding. Ligand L' is formed from an intramolecular attack of the alcoholic OH group of L to one imine moiety leading to the formation of a stereochemically constrained five-membered ring. Ligand L" which is formed from an intermolecular reaction involving one imine moiety of L and pyridine-2-carbaldehyde has an emissive cationic imidazopyridine pendant arm. The complex binds to double-stranded DNA in the minor groove giving a Kapp value of 4.1 x 10(5) M(-1) and displays oxidative cleavage of supercoiled DNA in the presence of H2O2 following a hydroxyl radical pathway. The complex also shows photo-induced DNA cleavage activity on UV light exposure involving formation of singlet oxygen as the reactive species.

NHC Versus Pyridine: How “Teeth” Change the Redox Behavior of Iron(II) Complexes

KAUST Repository

Weiss, Daniel T.

2015-10-06

A series of octahedral iron(II) complexes with tetradentate NHC/pyridine hybrid ligands containing up to three pyridyl units was designed to study the influence of NHC and pyridine donors on the electronic structure of the metal center. Structural analysis of the iron complexes by NMR spectroscopy and single-crystal X-ray diffraction reveals different coordination modes of the ligand depending on the linkage of the different donor moieties. The oxidation potentials of all complexes correlate linearly with the number of NHC moieties coordinated to iron, as shown by cyclic voltammetry. The influence, although minor, of structural properties on the oxidation potential and (in one case) the influence of the oxidation state of the coordination geometry of the hybrid ligand are also demonstrated.

Synthesis, characterization, and reactivity of furan- and thiophene-functionalized bis(n-heterocyclic carbene) complexes of iron(II)

KAUST Repository

Rieb, Julia

2014-09-15

The synthesis of iron(II) complexes bearing new heteroatom-functionalized methylene-bridged bis(N-heterocyclic carbene) ligands is reported. All complexes are characterized by single-crystal X-ray diffraction (SC-XRD), nuclear magnetic resonance (NMR) spectroscopy, and elemental analysis. Tetrakis(acetonitrile)-cis-[bis(o-imidazol-2-ylidenefuran)methane]iron(II) hexafluorophosphate (2a) and tetrakis(acetonitrile)-cis-[bis(o-imidazol-2-ylidenethiophene)methane]iron(II) hexafluorophosphate (2b) were obtained by aminolysis of [Fe{N(SiMe3)2}2(THF)] with furan- and thiophene-functionalized bis(imidazolium) salts 1a and 1b in acetonitrile. The SC-XRD structures of 2a and 2b show coordination of the bis(carbene) ligand in a bidentate fashion instead of a possible tetradentate coordination. The four other coordination sites of these distorted octahedral complexes are occupied by acetonitrile ligands. Crystallization of 2a in an acetone solution by the slow diffusion of Et2O led to the formation of cisdiacetonitriledi[ bis(o-imidazol-2-ylidenefuran)methane]iron(II) hexafluorophosphate (3a) with two bis(carbene) ligands coordinated in a bidentate manner and two cis-positioned acetonitrile molecules. Compounds 2a and 2b are the first reported iron(II) carbene complexes with four coordination sites occupied by solvent molecules, and it was demonstrated that those solvent ligands can undergo ligand-exchange reactions.

Mechanism of redox reactions induced by light and electron pulse in solutions of mixed ligand iron(II) complex cyanides

International Nuclear Information System (INIS)

Horvath, A.; Szoeke, J.; Wojnarovits, L.

1991-01-01

Redox reactions induced by light and electron pulse have been studied in aqueous solutions of mixed ligand iron(II) complex cyanides. The short lived intermediates have been identified by time resolved specroscopy, the results of detailed kinetic analysis have been discussed. (author) 6 refs.; 3 figs.; 2 tabs

Dimerization of Terminal Aryl Alkynes Catalyzed by Iron(II) Amine-Pyrazolyl Tripodal Complexes with E/Z Selectivity Controlled by tert-Butoxide

KAUST Repository

Xue, Fei

2018-05-09

The catalytic activity of iron(II) complexes with functionalized amine-pyrazolyl tripodal ligands toward dimerization of terminal alkynes in the presence a base (KOtBu or NaOtBu) has been studied. An unusual E/Z selectivity of the reaction determined by tert-butoxide was observed.

Dimerization of Terminal Aryl Alkynes Catalyzed by Iron(II) Amine-Pyrazolyl Tripodal Complexes with E/Z Selectivity Controlled by tert-Butoxide

KAUST Repository

Xue, Fei; Song, Xiaolu; Lin, Ting Ting; Munkerup, Kristin; Albawardi, Saad Fahad; Huang, Kuo-Wei; Hor, T. S. Andy; Zhao, Jin

2018-01-01

The catalytic activity of iron(II) complexes with functionalized amine-pyrazolyl tripodal ligands toward dimerization of terminal alkynes in the presence a base (KOtBu or NaOtBu) has been studied. An unusual E/Z selectivity of the reaction determined by tert-butoxide was observed.

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...

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.

Complex Metal Hydrides for hydrogen storage and solid-state ion conductors

DEFF Research Database (Denmark)

Payandeh GharibDoust, SeyedHosein

and electricity in batteries. However, both hydrogen and electricity must be stored in a very dense way to be useful, e.g. for mobile applications. Complex metal hydrides have high hydrogen density and have been studied during the past twenty years in hydrogen storage systems. Moreover, they have shown high ionic...... conductivities which promote their application as solid electrolytes in batteries. This dissertation presents the synthesis and characterization of a variety of complex metal hydrides and explores their hydrogen storage properties and ionic conductivity. Five halide free rare earth borohydrides RE(BH4)3, (RE...... = La, Ce, Pr, Nd, Er) have been synthesized, which pave the way for studying the polymorphic transition in these compounds, obtaining new bimetallic borohydrides and designing new reactive hydride composites with improved hydrogen storage capacities. Two novel polymorphs of Pr(BH4)3 are identified...

Enhancement of Hydrogen Storage Behavior of Complex Hydrides via Bimetallic Nanocatalysts Doping

Directory of Open Access Journals (Sweden)

Prakash C. Sharma

2012-10-01

Full Text Available Pristine complex quaternary hydride (LiBH4/2LiNH2 and its destabilized counterpart (LiBH4/2LiNH2/nanoMgH2 have recently shown promising reversible hydrogen storage capacity under moderate operating conditions. The destabilization of complex hydride via nanocrystalline MgH2 apparently lowers the thermodynamic heat values and thus enhances the reversible hydrogen storage behavior at moderate temperatures. However, the kinetics of these materials is rather low and needs to be improved for on-board vehicular applications. Nanocatalyst additives such as nano Ni, nano Fe, nano Co, nano Mn and nano Cu at low concentrations on the complex hydride host structures have demonstrated a reduction in the decomposition temperature and overall increase in the hydrogen desorption reaction rates. Bi-metallic nanocatalysts such as the combination of nano Fe and nano Ni have shown further pronounced kinetics enhancement in comparison to their individual counterparts. Additionally, the vital advantage of using bi-metallic nanocatalysts is to enable the synergistic effects and characteristics of the two transitional nanometal species on the host hydride matrix for the optimized hydrogen storage behavior.

Iron(II) tris(3-bromo-1,10-phenanthroline) complex:synthesis, crystal structure and electropolymerization

CERN Document Server

Lee, K J; Lee, S S; Lee, B Y

2002-01-01

The complex of iron(II) tris(3-Br-phen)(3-Br-phen; 3-bromo-1,10-phenanthroline) was prepared as a precursor of electropolymerization and the crystal structure of [Fe(3-Br-phen) sub 3](PF sub 6) sub 2 centre dot CH sub 3 CN with a distorted octahedral geometry has been investigated. The reductive electropolymerization of [Fe(3-Br-phen) sub 3] sup 2 sup + complex onto the surface of a glassy carbon electrode and indium tin oxide (ITO) optically transparent electrode were performed in acetonitrile at room temperature. Thin film of poly-[Fe(3-Br-phen) sub 3] sup 2 sup + formed was adherent, electroactive and stably deposited on a glassy carbon disk electrode. The thin metallopolymeric film formed was also confirmed by absorption spectroscopy.

Oxidative degradation of the organometallic iron(II) complex [Fe{bis[3-(pyridin-2-yl)-1H-imidazol-1-yl]methane}(MeCN)(PMe3)](PF6)2: structure of the ligand decomposition product trapped via coordination to iron(II).

Science.gov (United States)

Haslinger, Stefan; Pöthig, Alexander; Cokoja, Mirza; Kühn, Fritz E

2015-12-01

Iron is of interest as a catalyst because of its established use in the Haber-Bosch process and because of its high abundance and low toxicity. Nitrogen-heterocyclic carbenes (NHC) are important ligands in homogeneous catalysis and iron-NHC complexes have attracted increasing attention in recent years but still face problems in terms of stability under oxidative conditions. The structure of the iron(II) complex [1,1'-bis(pyridin-2-yl)-2,2-bi(1H-imidazole)-κN(3)][3,3'-bis(pyridin-2-yl-κN)-1,1'-methanediylbi(1H-imidazol-2-yl-κC(2))](trimethylphosphane-κP)iron(II) bis(hexafluoridophosphate), [Fe(C17H14N6)(C16H12N6)(C3H9P)](PF6)2, features coordination by an organic decomposition product of a tetradentate NHC ligand in an axial position. The decomposition product, a C-C-coupled biimidazole, is trapped by coordination to still-intact iron(II) complexes. Insights into the structural features of the organic decomposition products might help to improve the stability of oxidation catalysts under harsh conditions.

Development of Hydrogen Storage Tank Systems Based on Complex Metal Hydrides

Directory of Open Access Journals (Sweden)

Morten B. Ley

2015-09-01

Full Text Available This review describes recent research in the development of tank systems based on complex metal hydrides for thermolysis and hydrolysis. Commercial applications using complex metal hydrides are limited, especially for thermolysis-based systems where so far only demonstration projects have been performed. Hydrolysis-based systems find their way in space, naval, military and defense applications due to their compatibility with proton exchange membrane (PEM fuel cells. Tank design, modeling, and development for thermolysis and hydrolysis systems as well as commercial applications of hydrolysis systems are described in more detail in this review. For thermolysis, mostly sodium aluminum hydride containing tanks were developed, and only a few examples with nitrides, ammonia borane and alane. For hydrolysis, sodium borohydride was the preferred material whereas ammonia borane found less popularity. Recycling of the sodium borohydride spent fuel remains an important part for their commercial viability.

Development of Hydrogen Storage Tank Systems Based on Complex Metal Hydrides

Science.gov (United States)

Ley, Morten B.; Meggouh, Mariem; Moury, Romain; Peinecke, Kateryna; Felderhoff, Michael

2015-01-01

This review describes recent research in the development of tank systems based on complex metal hydrides for thermolysis and hydrolysis. Commercial applications using complex metal hydrides are limited, especially for thermolysis-based systems where so far only demonstration projects have been performed. Hydrolysis-based systems find their way in space, naval, military and defense applications due to their compatibility with proton exchange membrane (PEM) fuel cells. Tank design, modeling, and development for thermolysis and hydrolysis systems as well as commercial applications of hydrolysis systems are described in more detail in this review. For thermolysis, mostly sodium aluminum hydride containing tanks were developed, and only a few examples with nitrides, ammonia borane and alane. For hydrolysis, sodium borohydride was the preferred material whereas ammonia borane found less popularity. Recycling of the sodium borohydride spent fuel remains an important part for their commercial viability. PMID:28793541

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.

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

Science.gov (United States)

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

2016-02-01

Solid-state hydrogen storage using various materials is expected to provide the ultimate solution for safe and efficient on-board storage. Complex hydrides have attracted increasing attention over the past two decades due to their high gravimetric and volumetric hydrogen densities. In this account, we review studies from our lab on tailoring the thermodynamics and kinetics for hydrogen storage in complex hydrides, including metal alanates, borohydrides and amides. By changing the material composition and structure, developing feasible preparation methods, doping high-performance catalysts, optimizing multifunctional additives, creating nanostructures and understanding the interaction mechanisms with hydrogen, the operating temperatures for hydrogen storage in metal amides, alanates and borohydrides are remarkably reduced. This temperature reduction is associated with enhanced reaction kinetics and improved reversibility. The examples discussed in this review are expected to provide new inspiration for the development of complex hydrides with high hydrogen capacity and appropriate thermodynamics and kinetics for hydrogen storage. © 2015 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Iron(II) porphyrins induced conversion of nitrite into nitric oxide: A computational study.

Science.gov (United States)

Zhang, Ting Ting; Liu, Yong Dong; Zhong, Ru Gang

2015-09-01

Nitrite reduction to nitric oxide by heme proteins was reported as a protective mechanism to hypoxic injury in mammalian physiology. In this study, the pathways of nitrite reduction to nitric oxide mediated by iron(II) porphyrin (P) complexes, which were generally recognized as models for heme proteins, were investigated by using density functional theory (DFT). In view of two type isomers of combination of nitrite and Fe(II)(P), N-nitro- and O-nitrito-Fe(II)-porphyrin complexes, and two binding sites of proton to the different O atoms of nitrite moiety, four main pathways for the conversion of nitrite into nitric oxide mediated by iron(II) porphyrins were proposed. The results indicate that the pathway of N-bound Fe(II)(P)(NO2) isomer into Fe(III)(P)(NO) and water is similar to that of O-bound isomer into nitric oxide and Fe(III)(P)(OH) in both thermodynamical and dynamical aspects. Based on the initial computational studies of five-coordinate nitrite complexes, the conversion of nitrite into NO mediated by Fe(II)(P)(L) complexes with 14 kinds of proximal ligands was also investigated. Generally, the same conclusion that the pathways of N-bound isomers are similar to those of O-bound isomer was obtained for iron(II) porphyrin with ligands. Different effects of ligands on the reduction reactions were also found. It is notable that the negative proximal ligands can improve reactive abilities of N-nitro-iron(II) porphyrins in the conversion of nitrite into nitric oxide compared to neutral ligands. The findings will be helpful to expand our understanding of the mechanism of nitrite reduction to nitric oxide by iron(II) porphyrins. Copyright © 2015 Elsevier Inc. All rights reserved.

Iron(II) complexes of new hexadentate 1,1,1-tris-(iminomethyl)ethane podands, and their 7-methyl-1,3,5-triazaadamantane rearrangement products.

Science.gov (United States)

Diener, Sara A; Santoro, Amedeo; Kilner, Colin A; Loughrey, Jonathan J; Halcrow, Malcolm A

2012-04-07

New iron(II) podand complexes have been prepared, by condensation of 2-(aminomethyl)-2-methyl-1,3-diaminopropane with 3 equiv of a heterocyclic aldehyde in the presence of hydrated Fe[BF(4)](2) or Fe[ClO(4)](2) as templates. The 2-(aminomethyl)-2-methyl-1,3-diaminopropane is prepared in situ by deprotonation of its trihydrochloride salt. The chloride must be removed from these reactions by precipitation with silver, to avoid the formation of the alternative 2,4,6-trisubstituted-7-methyl-1,3,5-triazaadamantane condensation products, or their FeCl(2) adducts. The crystal structures of two 2,4,6-tri(pyridyl)-7-methyl-1,3,5-triazaadamantane-containing species are presented, and contain two different geometric isomers of this tricyclic ring with three equatorial, or two equatorial and one axial, pyridyl substituents. Both structures feature strong C-HX (X = Cl or F) hydrogen bonding from the aminal C-H groups in the triazaadamantane ring. Five iron(II) podand complexes were successfully obtained, all of which contain low-spin iron centres.

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)

Making oxidation potentials predictable: Coordination of additives applied to the electronic fine tuning of an iron(II) complex

KAUST Repository

Haslinger, Stefan

2014-11-03

This work examines the impact of axially coordinating additives on the electronic structure of a bioinspired octahedral low-spin iron(II) N-heterocyclic carbene (Fe-NHC) complex. Bearing two labile trans-acetonitrile ligands, the Fe-NHC complex, which is also an excellent oxidation catalyst, is prone to axial ligand exchange. Phosphine- and pyridine-based additives are used for substitution of the acetonitrile ligands. On the basis of the resulting defined complexes, predictability of the oxidation potentials is demonstrated, based on a correlation between cyclic voltammetry experiments and density functional theory calculated molecular orbital energies. Fundamental insights into changes of the electronic properties upon axial ligand exchange and the impact on related attributes will finally lead to target-oriented manipulation of the electronic properties and consequently to the effective tuning of the reactivity of bioinspired systems.

Making oxidation potentials predictable: Coordination of additives applied to the electronic fine tuning of an iron(II) complex

KAUST Repository

Haslinger, Stefan; Kü ck, Jens W.; Hahn, Eva M.; Cokoja, Mirza; Pö thig, Alexander; Basset, Jean-Marie; Kü hn, Fritz

2014-01-01

This work examines the impact of axially coordinating additives on the electronic structure of a bioinspired octahedral low-spin iron(II) N-heterocyclic carbene (Fe-NHC) complex. Bearing two labile trans-acetonitrile ligands, the Fe-NHC complex, which is also an excellent oxidation catalyst, is prone to axial ligand exchange. Phosphine- and pyridine-based additives are used for substitution of the acetonitrile ligands. On the basis of the resulting defined complexes, predictability of the oxidation potentials is demonstrated, based on a correlation between cyclic voltammetry experiments and density functional theory calculated molecular orbital energies. Fundamental insights into changes of the electronic properties upon axial ligand exchange and the impact on related attributes will finally lead to target-oriented manipulation of the electronic properties and consequently to the effective tuning of the reactivity of bioinspired systems.

Synthesis and Ligand Non-Innocence of Thiolate-Ligated (N4S) Iron(II) and Nickel(II) Bis(imino)pyridine Complexes

Science.gov (United States)

Widger, Leland R.; Jiang, Yunbo; Siegler, Maxime; Kumar, Devesh; Latifi, Reza; de Visser, Sam P.; Jameson, Guy N.L.; Goldberg, David P.

2013-01-01

The known iron(II) complex [FeII(LN3S)(OTf)] (1) was used as starting material to prepare the new biomimetic (N4S(thiolate)) iron(II) complexes [FeII(LN3S)(py)](OTf) (2) and [FeII(LN3S)(DMAP)](OTf) (3), where LN3S is a tetradentate bis(imino)pyridine (BIP) derivative with a covalently tethered phenylthiolate donor. These complexes were characterized by X-ray crystallography, UV-vis, 1H NMR, and Mössbauer spectroscopy, as well as electrochemistry. A nickel(II) analogue, [NiII(LN3S)](BF4) (5), was also synthesized and characterized by structural and spectroscopic methods. Cyclic voltammetric studies showed 1 – 3 and 5 undergo a single reduction process with E1/2 between −0.9 to −1.2 V versus Fc+/Fc. Treatment of 3 with 0.5% Na/Hg amalgam gave the mono-reduced complex [Fe(LN3S)(DMAP)]0 (4), which was characterized by X-ray crystallography, UV-vis, EPR (g = [2.155, 2.057, 2.038]) and Mössbauer (δ = 0.33 mm s−1; ΔEQ = 2.04 mm s−1) spectroscopies. Computational methods (DFT) were employed to model complexes 3 – 5. The combined experimental and computational studies show that 1 – 3 are 5-coordinate, high-spin (S = 2) FeII complexes, whereas 4 is best described as a 5-coordinate, intermediate-spin (S = 1) FeII complex antiferromagnetically coupled to a ligand radical. This unique electronic configuration leads to an overall doublet spin (Stotal = ½) ground state. Complexes 2 and 3 are shown to react with O2 to give S-oxygenated products, as previously reported for 1. In contrast, the mono-reduced 4 appears to react with O2 to give a mixture of S- and Fe-oxygenates. The nickel(II) complex 5 does not react with O2, and even when the mono-reduced nickel complex is produced, it appears to undergo only outer-sphere oxidation with O2. PMID:23992096

Interesting properties of some iron(II), copper(I) and copper(II ...

Indian Academy of Sciences (India)

Administrator

Tridendate ligands with nitrogen centers, generally well-known as the tripod ligands, have been of considerable interest to inorganic chemists dealing with the preparation of model compounds for hemocyanin, tyrosinase etc. We have found that such ligands when complexed with iron(II) and copper(II) and copper(I) ions ...

High Density Hydrogen Storage System Demonstration Using NaAlH4 Based Complex Compound Hydrides

Energy Technology Data Exchange (ETDEWEB)

Daniel A. Mosher; Xia Tang; Ronald J. Brown; Sarah Arsenault; Salvatore Saitta; Bruce L. Laube; Robert H. Dold; Donald L. Anton

2007-07-27

This final report describes the motivations, activities and results of the hydrogen storage independent project "High Density Hydrogen Storage System Demonstration Using NaAlH4 Based Complex Compound Hydrides" performed by the United Technologies Research Center under the Department of Energy Hydrogen Program, contract # DE-FC36-02AL67610. The objectives of the project were to identify and address the key systems technologies associated with applying complex hydride materials, particularly ones which differ from those for conventional metal hydride based storage. This involved the design, fabrication and testing of two prototype systems based on the hydrogen storage material NaAlH4. Safety testing, catalysis studies, heat exchanger optimization, reaction kinetics modeling, thermochemical finite element analysis, powder densification development and material neutralization were elements included in the effort.

Structural stability of complex hydrides LiBH₄ revisited

DEFF Research Database (Denmark)

Lodziana, Zbigniew; Vegge, Tejs

2004-01-01

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

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.

Stress-induced reorientation of hydride precipitates in Zr-2.5Nb-0.5Cu garter springs under complex loading

International Nuclear Information System (INIS)

De, P.K.; John, J.T.; Raman, V.V.; Banerjee, S.

1991-01-01

Zr-2.5Nb-0.5Cu garter springs which are placed between coolant and calandria tubes in PHWRs experience complex loading due to simultaneous application of tension, compression and torus bending moment due to coolant tubes. The gradual pick up of hydrogen by the garter springs during service is likely to have hydride platelets reoriented under the applied stresses. In the present paper, the magnitudes and the directions of the principal stresses under the complex loading condition obtained have been calculated and the extent of hydride reorientation predicted. Simulation experiments consisting of simulated loading of hydrogen (upto 400 ppm) precharged springs at the service temperature (300degC) and also in-situ hydrogen charging of the springs under simulated loading conditions have been carried out. In addition, hydrogen precharged springs have been subjected to temperature cycling between 50 and 300degC under complex loading conditions, to evaluate the influence of temperature variation on hydride reorientation. Metallographic examination of the hydride platelets in the above springs has shown an excellent agreement with the analytical prediction. Torus bending moment values appear to play a significant role in reorienting the hydride platelets. It has been observed that under normal torus bending moment corresponding to 90 mm dia coolant tubes hydrogen platelets close to the outer rim of the spiral get reoriented in the radial direction. However, on application a torus bending moment corresponding to 30 mm dia tubes, hydride platelets get reoriented along the radial direction, irrespective of the magnitude of tensile and compression loading. (author). 9 refs., 15 figs., 1 appendix

Expanding Thorium Hydride Chemistry Through Th²⁺, Including the Synthesis of a Mixed-Valent Th⁴⁺/Th³⁺ Hydride Complex.

Science.gov (United States)

Langeslay, Ryan R; Fieser, Megan E; Ziller, Joseph W; Furche, Filipp; Evans, William J

2016-03-30

The reactivity of the recently discovered Th(2+) complex [K(18-crown-6)(THF)2][Cp″3Th], 1 [Cp'' = C5H3(SiMe3)2-1,3], with hydrogen reagents has been investigated and found to provide syntheses of new classes of thorium hydride compounds. Complex 1 reacts with [Et3NH][BPh4] to form the terminal Th(4+) hydride complex Cp″3ThH, 2, a reaction that formally involves a net two-electron reduction. Complex 1 also reacts in the solid state and in solution with H2 to form a mixed-valent bimetallic product, [K(18-crown-6)(Et2O)][Cp″2ThH2]2, 3, which was analyzed by X-ray crystallography, electron paramagnetic resonance and optical spectroscopy, and density functional theory. The existence of 3, which formally contains Th(3+) and Th(4+), suggested that KC8 could reduce [(C5Me5)2ThH2]2. In the presence of 18-crown-6, this reaction forms an analogous mixed-valent product formulated as [K(18-crown-6)(THF)][(C5Me5)2ThH2]2, 4. A similar complex with (C5Me4H)(1-) ligands was not obtained, but reaction of (C5Me4H)3Th with H2 in the presence of KC8 and 2.2.2-cryptand at -45 °C produced two monometallic hydride products, namely, (C5Me4H)3ThH, 5, and [K(2.2.2-cryptand)]{(C5Me4H)2[η(1):η(5)-C5Me3H(CH2)]ThH]}, 6. Complex 6 contains a metalated tetramethylcyclopentadienyl dianion, [C5Me3H(CH2)](2-), that binds in a tuck-in mode.

Synthesis, characterization and single crystal x-ray analysis of a complex of iron(II) bis(2,4-dimethylphenyl)dithiophosphate with 4-ethylpyridine

Energy Technology Data Exchange (ETDEWEB)

Kumar, Sandeep; Andotra, Savit; Kaur, Mandeep [University of Jammu, Department of Chemistry (India); Gupta, Vivek K.; Kant, Rajni [Department of Physics and Electronics, University of Jammu, X-ray Crystallographic Laboratory (India); Pandey, Sushil K., E-mail: kpsushil@rediffmail.com [University of Jammu, Department of Chemistry (India)

2016-09-15

Complex of iron(II) bis(2,4-dimethylphenyl)dithiophosphate with 4-ethylpyridine [((2,4- (CH{sub 3}){sub 2}C{sub 6}H{sub 3}O)2PS2)2Fe(NC{sub 5}H{sub 4}(C{sub 2}H{sub 5})-4){sub 2}] is synthesized and characterized by elemental analysis, magnetic moment, IR spectroscopy and single crystal X-ray analysis. Complex crystallizes in the monoclinic sp. gr. P2{sub 1}/n, Z = 2. Crystal structure consists of mononuclear units with Fe(II) ion chelated by four S atoms of the two diphenyldithiophosphate ligands in bidentate manner. N atoms from two 4-ethylpyridine ligands are axially coordinated to the Fe(II) atom leading to an octahedral geometry.

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.

Design and synthesis of a tetradentate '3-amine-1-carboxylate' ligand to mimic the metal binding environment at the non-heme iron(II) oxidase active site.

Science.gov (United States)

Dungan, Victoria J; Ortin, Yannick; Mueller-Bunz, Helge; Rutledge, Peter J

2010-04-07

Non-heme iron(II) oxidases (NHIOs) catalyse a diverse array of oxidative chemistry in Nature. As part of ongoing efforts to realize biomimetic, iron-mediated C-H activation, we report the synthesis of a new 'three-amine-one-carboxylate' ligand designed to complex with iron(II) and mimic the NHIO active site. The tetradentate ligand has been prepared as a single enantiomer in nine synthetic steps from N-Cbz-L-alanine, pyridine-2,6-dimethanol and diphenylamine, using Seebach oxazolidinone chemistry to control the stereochemistry. X-Ray crystal structures are reported for two important intermediates, along with variable temperature NMR experiments to probe the hindered interconversion of conformational isomers of several key intermediates, 2,6-disubstituted pyridine derivatives. The target ligand and an N-Cbz-protected precursor were each then complexed with iron(II) and tested for their ability to promote alkene dihydroxylation, using hydrogen peroxide as the oxidant.

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

INTERACTION OF IRON(II MIXED-LIGAND COMPLEXES WITH DNA: BASE-PAIR SPECIFICITY AND THERMAL DENATURATION STUDIES

Directory of Open Access Journals (Sweden)

Mudasir Mudasir

2010-06-01

Full Text Available A research about base-pair specificity of the DNA binding of [Fe(phen3]2+, [Fe(phen2(dip]2+ and [Fe(phen(dip2]2+ complexes and the effect of calf-thymus DNA (ct-DNA binding of these metal complexes on thermal denaturation of ct-DNA has been carried out. This research is intended to evaluate the preferential binding of the complexes to the sequence of DNA (A-T or G-C sequence and to investigate the binding strength and mode upon their interaction with DNA. Base-pair specificity of the DNA binding of the complexes was determined by comparing the equilibrium binding constant (Kb of each complex to polysynthetic DNA that contain only A-T or G-C sequence. The Kb value of the interaction was determined by spectrophotometric titration and thermal denaturation temperature (Tm was determined by monitoring the absorbance of the mixture solution of each complex and ct-DNA at λ =260 nm as temperature was elevated in the range of 25 - 100 oC. Results of the study show that in general all iron(II complexes studied exhibit a base-pair specificity in their DNA binding to prefer the relatively facile A-T sequence as compared to the G-C one. The thermal denaturation experiments have demonstrated that Fe(phen3]2+ and [Fe(phen2(dip]2+ interact weakly with double helical DNA via electrostatic interaction as indicated by insignificant changes in melting temperature, whereas [Fe(phen2(dip]2+  most probably binds to DNA in mixed modes of interaction, i.e.: intercalation and electrostatic interaction. This conclusion is based on the fact that the binding of [Fe(phen2(dip]2+ to ct-DNA moderately increase the Tm value of ct- DNA   Keywords: DNA Binding, mixed-ligand complexes

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

Ammonia from iron(II) reduction of nitrite and the Strecker synthesis: do iron(II) and cyanide interfere with each other?

Science.gov (United States)

Summers, D. P.; Lerner, N.

1998-01-01

The question of whether the production of ammonia, from the reduction of nitrite by iron(II), is compatible with its use in the Strecker synthesis of amino acids, or whether the iron and the cyanide needed for the Strecker synthesis interfere with each other, is addressed. Results show that the presence of iron(II) appears to have little, or no, effect on the Strecker synthesis. The presence of cyanide does interfere with reduction of nitrite, but the reduction proceeds at cyanide/iron ratios of less than 4:1. At ratios of about 2:1 and less there is only a small effect. The reduction of nitrite and the Strecker can be combined to proceed in each other's presence, to yield glycine from a mixture of nitrite, Fe+2, formaldehyde, and cyanide.

Preservation of iron(II) by carbon-rich matrices in a hydrothermal plume

Energy Technology Data Exchange (ETDEWEB)

Toner, Brandy M.; Fakra, Sirine C.; Manganini, Steven J.; Santelli, Cara M.; Marcus, Matthew A.; Moffett, James W.; Rouxel, Olivier; German, Christopher R.; Edwards, Katrina J.

2008-09-20

Hydrothermal venting associated with mid-ocean ridge volcanism is globally widespread. This venting is responsible for a dissolved iron flux to the ocean that is approximately equal to that associated with continental riverine runoff. For hydrothermal fluxes, it has long been assumed that most of the iron entering the oceans is precipitated in inorganic forms. However, the possibility of globally significant fluxes of iron escaping these mass precipitation events and entering open-ocean cycles is now being debated, and two recent studies suggest that dissolved organic ligands might influence the fate of hydrothermally vented metals. Here we present spectromicroscopic measurements of iron and carbon in hydrothermal plume particles at the East Pacific Rise mid-ocean ridge. We show that organic carbon-rich matrices, containing evenly dispersed iron(II)-rich materials, are pervasive in hydrothermal plume particles. The absence of discrete iron(II) particles suggests that the carbon and iron associate through sorption or complexation. We suggest that these carbon matrices stabilize iron(II) released from hydrothermal vents in the region, preventing its oxidation and/or precipitation as insoluble minerals. Our findings have implications for deep-sea biogeochemical cycling of iron, a widely recognized limiting nutrient in the oceans.

Multisensor system for determination of iron(II), iron(III), uranium(VI) and uranium(IV) in complex solutions

International Nuclear Information System (INIS)

Legin, A.V.; Seleznev, B.L.; Rudnitskaya, A.M.; Vlasov, Yu.G.; Tverdokhlebov, S.V.; Mack, B.; Abraham, A.; Arnold, T.; Baraniak, L.; Nitsche, H.

1999-01-01

Development and analytical evaluation of a multisensor system based on the principles of 'electronic tongue' for the determination of low contents of uranium(VI), uranium(IV), iron(II) and iron(III) in complex aqueous media have been carried out. A set of 29 different chemical sensors on the basis of all- solid-state crystalline and vitreous materials with enhanced electronic conductivity and redox and ionic cross-sensitivity have been incorporated into the sensor array. Multidimensional data have been processed by pattern recognition methods such as artificial neural networks and partial least squares. It has been demonstrated that Fe(II) and Fe(III) contents in the range from 10 -7 to 10 -4 mol L -1 of total iron concentration can be determined with the average precision of about 25 %. U(VI) and U(IV) contents can been determined with the average precision of 10-40% depending on the concentration. The developed multisensor system can be applied in future for the analysis of mining and borehole waters as well other contaminated natural media, including on-site measurements. (author)

The determination of arsenic, selenium, antimony, and tin in complex environmental samples by hydride generation AAS

International Nuclear Information System (INIS)

Johnson, D.; Beach, C.

1990-01-01

Hydride generation techniques are used routinely for the determination of As, Se, Sb and Sn in water samples. Advantages include high sensitivity, simplicity, and relative freedom from interferences. Continuous-flow designs greatly reduce analysis time as well as improve precision and allow for automation. However the accurate analysis of more complex environmental samples such as industrial sludges, soil samples, river sediments, and fly ash remains difficult. Numerous contributing factors influence the accuracy of the hydride technique. Sample digestion methods and sample preparation procedures are of critical importance. The digestion must adequately solubilize the elements of interest without loss by volatilization. Sample preparation procedures that guarantee the proper analyte oxidation state and eliminate the nitric acid and inter-element interferences are needed. In this study, difficult environmental samples were analyzed for As, Se, Sb, and Sn by continuous flow hydride generation. Sample preparation methods were optimized to eliminate interferences. The results of spike recovery studies will be presented. Data from the analysis of the same samples by graphite furnace AAS will be presented for comparison of accuracy, precision, and analysis time

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)

Inorganic arsenic and iron(II) distributions in sediment porewaters investigated by a combined DGTcolourimetric DET technique

DEFF Research Database (Denmark)

Bennett, William W.; Teasdale, Peter R.; Welsh, David T.

2012-01-01

A new approach for investigating the biogeochemistry of inorganic arsenic and iron(II) in freshwater, estuarine and marine sediments is reported. The recently developed Metsorb diffusive gradients in thin films (DGT) technique for the measurement of total inorganic arsenic and the colourimetric d...... highly representative assessment of the biogeochemical status of arsenic and iron in a variety of natural sediments, including groundwater sediments where mobilised arsenic is responsible for significant human health risks.......A new approach for investigating the biogeochemistry of inorganic arsenic and iron(II) in freshwater, estuarine and marine sediments is reported. The recently developed Metsorb diffusive gradients in thin films (DGT) technique for the measurement of total inorganic arsenic and the colourimetric...... diffusive equilibration in thin films (DET) technique for the measurement of iron(II), were utilised in combination to determine co-located depth profiles of both solutes in sediment porewaters. DGT-measured porewater arsenic concentrations were typically less than 40nM, whereas iron(II) concentrations...

Complex transition metal hydrides incorporating ionic hydrogen: Synthesis and characterization of Na{sub 2}Mg{sub 2}FeH{sub 8} and Na{sub 2}Mg{sub 2}RuH{sub 8}

Energy Technology Data Exchange (ETDEWEB)

Humphries, Terry D., E-mail: terry_humphries81@hotmail.com [WPI-Advanced Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan); Takagi, Shigeyuki; Li, Guanqiao; Matsuo, Motoaki; Sato, Toyoto [Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan); Sørby, Magnus H.; Deledda, Stefano; Hauback, Bjørn C. [Physics Department, Institute for Energy Technology, Kjeller NO-2027 (Norway); Orimo, Shin-ichi [WPI-Advanced Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan); Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan)

2015-10-05

Highlights: • Structures of Na{sub 2}Mg{sub 2}FeH{sub 8} and Na{sub 2}Mg{sub 2}RuH{sub 8} have been determined by XRD and PND. • Compounds incorporate independently coordinated ionic and covalent hydrogen. • [TH{sub 6}]{sup 4−} anion is surrounded by a cubic array of four Mg{sup 2+} and four Na{sup +} cations. • H{sup −} anions are octahedrally coordinated by four Na{sup +} and two Mg{sup 2+} cations. • Vibrational modes of the H{sup −} anions and complex hydride anion are observed. - Abstract: A new class of quaternary complex transition metal hydrides (Na{sub 2}Mg{sub 2}TH{sub 8} (T = Fe, Ru)) have been synthesized and their structures determined by combined synchrotron radiation X-ray and powder neutron diffraction. The compounds can be considered as a link between ionic and complex hydrides in terms of incorporating independently coordinated ionic and covalent hydrogen. These novel isostructural complex transition metal hydrides crystallize in the orthorhombic space group Pbam, where the octahedral complex hydride anion is surrounded by a cubic array of four Mg{sup 2+} and four Na{sup +} cations, forming distinct two-dimensional layers. An intriguing feature of these materials is the distorted octahedral coordination of the isolated H{sup −} anions by four Na{sup +} and two Mg{sup 2+} cations, which form layers between the transition metal containing layers. The vibrational modes of the H{sup −} anions and complex hydride anion are independently observed for the first time in a quaternary complex transition metal hydride system by Raman and IR spectroscopy.

Orbital energies and structural non-rigidity of complex hydrides according to data on ab initio calculations

Energy Technology Data Exchange (ETDEWEB)

Boldyrev, A I; Sukhanov, L P; Charkin, O P [AN SSSR, Moscow. Inst. Novykh Khimicheskikh Problem

1982-01-01

In approximation by the Hartree-Fock-Routine method using several Gauss type bases ionization potentials of complex hydrides LiBeH/sub 3/, NaBeH/sub 3/, LiMgH/sub 3/, LiBH/sub 4/, NaBH/sub 4/ and LiAlH/sub 4/ have been calculated. A problem of the show of structural non-rigidity of complex molecules L(MX/sub 4/) with tetrahedral anions (MX/sub 4/)/sup -/ in photoelectron spectra is considered.

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.

Ab initio investigation of structure and stability of complex hydrides of L(MH/sub 3/) type

Energy Technology Data Exchange (ETDEWEB)

Sukhanov, L P; Boldyrev, A I; Charkin, O P [Gosudarstvennyj Komitet po Ispol' zovaniyu Atomnoj Ehnergii SSSR, Moscow. Inst. Atomnoj Ehnergii; AN SSSR, Chernogolovka. Inst. Novykh Khimicheskikh Problem)

1980-01-01

The structure, stability, sections of potential surfaces (PS) of NaBeH/sub 3/ and LiMgH/sub 3/ complex hydrides are calculated in the framework of the non-empiric Hartry-Fock-Ruthan method using the two-exponential Roos-Siegbahn basis. The extreme PS points are clarified with a more complete and flexible two-exponential Huzinada-Dunning basis and polarization. It is shown that NaBeH/sub 3/, LiMgH/sub 3/, as well as the formerly studied LiBeH/sub 3/ complex, belong to the amount of globally tough, but ilocally nontough molecular systems. Migration barriers on the way of shifting the outerspheric cation relatively to the anion decrease in the LiBeH/sub 3/-NaBeH/sub 3/ series, while they rise in the LiBeH/sub 3/-LiMgH/sub 3/ series. The correlation between the deformation of the anion nuclear carcass and the polarization of its electronic structure under the cation effect, is stated. The nature of the chemical bond in LMH/sub 3/ complexes is investigated on the basis of analyzing the composition of localized molecuar orbitals. The problems of energetic and kinetic stability of LMH/sub 3/ hydrides to different types of monomolecular decomposition, are discussed.

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

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)

Li2 NH-LiBH4 : a Complex Hydride with Near Ambient Hydrogen Adsorption and Fast Lithium Ion Conduction.

Science.gov (United States)

Wang, Han; Cao, Hujun; Zhang, Weijin; Chen, Jian; Wu, Hui; Pistidda, Claudio; Ju, Xiaohua; Zhou, Wei; Wu, Guotao; Etter, Martin; Klassen, Thomas; Dornheim, Martin; Chen, Ping

2018-01-26

Complex hydrides have played important roles in energy storage area. Here a complex hydride made of Li 2 NH and LiBH 4 was synthesized, which has a structure tentatively indexed using an orthorhombic cell with a space group of Pna2 1 and lattice parameters of a=10.121, b=6.997, and c=11.457 Å. The Li 2 NH-LiBH 4 sample (in a molar ratio of 1:1) shows excellent hydrogenation kinetics, starting to absorb H 2 at 310 K, which is more than 100 K lower than that of pristine Li 2 NH. Furthermore, the Li + ion conductivity of the Li 2 NH-LiBH 4 sample is about 1.0×10 -5  S cm -1 at room temperature, and is higher than that of either Li 2 NH or LiBH 4 at 373 K. Those unique properties of the Li 2 NH-LiBH 4 complex render it a promising candidate for hydrogen storage and Li ion conduction. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Update: An efficient synthesis of poly(ethylene glycol)-supported iron(II) porphyrin using a click reaction and its application for the catalytic olefination of aldehydes

KAUST Repository

Chinnusamy, Tamilselvi R.; Rodionov, Valentin; Kü hn, Fritz; Reiser, Oliver

2012-01-01

The facile synthesis of polyethylene glycol (PEG)-immobilized iron(II) porphyrin using a copper-catalyzed azide-alkyne [3+2] cycloaddition "click" reaction is reported. The prepared complex 5 (PEG-C 51H 39FeN 7O) was found to be an efficient

Hydrogen storage properties of Na-Li-Mg-Al-H complex hydrides

International Nuclear Information System (INIS)

Tang Xia; Opalka, Susanne M.; Laube, Bruce L.; Wu Fengjung; Strickler, Jamie R.; Anton, Donald L.

2007-01-01

Lightweight complex hydrides have attracted attention for their high storage hydrogen capacity. NaAlH 4 has been widely studied as a hydrogen storage material for its favorable reversible operating temperature and pressure range for automotive fuel cell applications. The increased understanding of NaAlH 4 has led to an expanded search for high capacity materials in mixed alkali and akali/alkaline earth alanates. In this study, promising candidates in the Na-Li-Mg-Al-H system were evaluated using a combination of experimental chemistry, atomic modeling, and thermodynamic modeling. New materials were synthesized using solid state and solution based processing methods. Their hydrogen storage properties were measured experimentally, and the test results were compared with theoretical modeling assessments

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

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.

Multisensor system for determination of iron(II), iron(III) and uranium(VI) in complex solutions

International Nuclear Information System (INIS)

Legin, A.V.; Seleznev, B.L.; Rudnitskaya, A.M.; Vlasov, Yu.G.

1998-01-01

The aim of the present paper is the development and analytical evaluation of a multisensor system for determination of low content of iron(II), iron(III) and uranium(VI) in complex aqueous media. Sensor array included sensors on the basis of chalcogenide vitreous materials with redox and ionic cross-sensitivities, crystalline silver sulphide electrode, noble metal electrodes Pt, Au, Ag and redox sensor on the basis of oxide glass. Potentiometric measurements have been taken in a conventional electrochemical cell vs. a standard Ag/AgCl reference electrode. All measurements have been taken at room temperature. Calibration solutions contained UO 2 (NO 3 ) 2 in concentration range 10 -6 -1,610 -5 mol/L, K 3 Fe(CN) 6 and K 4 Fe(CN) 6 or FeSO 4 (NH 4 ) 2 SO 4 and FeCl 3 , with the ratio of Fe(II)/Fe(III) concentration from 100:1 to 1:100, the total concentration of Fe was 10 -4 and 10 -5 mol/L. All solutions have been made on the background electrolyte of calcium and magnesium chlorides and sulphates with the fixed content of 5-27 mmol/L of each component which is a typical one for groundwater or mining water. Sensor potentials have been processed by a back-propagation artificial neural net. Average error of determination of Fe(II) and Fe(III) is about 20 %, of uranium(VI) - 40 %. It was found that sensitivity of the sensor array to iron and uranium is irrespective of the chemical form of these species

The effect of stress state on zirconium hydride reorientation

Science.gov (United States)

Cinbiz, Mahmut Nedim

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

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

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.)

Optimization of colorimetric DET technique for the in situ, two-dimensional measurement of iron(II) distributions in sediment porewaters

DEFF Research Database (Denmark)

Bennett, William W.; Teasdale, Peter R.; Welsh, David T.

2012-01-01

The recently developed colorimetric diffusive equilibration in thin films (DET) technique for the in situ, high-resolution measurement of iron(II) in marine sediments is optimized to allow measurement of the higher iron concentrations typical of freshwater sediment porewaters. Computer imaging...... the sensitivity of the assay as required; by processing the image with different color channel filters, the sensitivity of the assay can be optimized for lower concentrations (up to 100 μmol L -1) or higher concentrations (up to 2000 μmol L -1) of iron(II), depending on the specific site characteristics......(II) in sediment porewaters. The detection limit of the optimized technique was 4.1 ± 0.3 μmol L -1 iron(II) and relative standard deviations were less than 6%....

Effects of Selected Dietary Secondary Metabolites on Reactive Oxygen Species Production Caused by Iron(II Autoxidation

Directory of Open Access Journals (Sweden)

Vladimir Chobot

2014-12-01

Full Text Available Iron is an essential co-factor for many enzymes that catalyze electron transfer reactions. It is well known that so-called “poorly liganded” iron can increase ROS concentrations and trigger oxidative stress that is capable of initiating apoptosis. Conversely, controlled ROS production has been recognized as an integral part of cellular signaling. Elevated ROS concentrations are associated with aging, inflammatory and degenerative diseases. Anti-aging properties have been attributed especially to antioxidant phenolic plant metabolites that represent food additives in our diet. Consequently, this study explores the effects of flavonoids (quercetin and rutin, several phenolic acids (caffeic, chlorogenic, and protocatechuic acid, and the alkaloid caffeine on iron(II autoxidation and ROS production in comparison to the standard antioxidants ascorbic acid and Trolox. The iron(II autoxidation assay was carried out in pH 6.0 (plant apoplast and inflamed human tissue and 7.4 (cell cytoplasm and human blood plasma. The obtained results accentuate phenolic acids as the more specific antioxidants compared to ascorbic acid and Trolox. Flavonoid redox chemistry depends more on the chemical milieu, specifically on pH. In vivo, the presence of iron cannot be ruled out and “wrongly” or “poorly” complexed iron has been pointed out as causative agent of various age-related diseases.

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)

High-Temperature Wide Thermal Hysteresis of an Iron(II Dinuclear Double Helicate

Directory of Open Access Journals (Sweden)

Shiori Hora

2017-07-01

Full Text Available Two new dinuclear iron(II complexes (1·PF6 and 1·AsF6 of the general formula [FeII2(L2C32](X4·nH2O·mMeCN (X = PF6, n = m = 1.5 for 1·PF6 and X = AsF6, n = 3, m = 1 for 1·AsF6 have been prepared and structurally characterized, where L2C3 is a bis-1,2,3-triazolimine type Schiff-base ligand, 1,1′-[propane-1,3-diylbis(1H-1,2,3-triazole-1,4-diyl]bis{N-[2-(pyridin-2-ylethyl]methanimine}. Single crystal X-ray structure analyses revealed that 1·PF6 and 1·AsF6 are isostructural. The complex-cation [FeII2(L2C32]4+ of both has the same dinuclear double helicate architecture, in which each iron(II center has an N6 octahedral coordination environment. Neighboring helicates are connected by intermolecular π–π interactions to give a chiral one-dimensional (1D structure, and cationic 1D chains with the opposite chirality exist in the crystal lattice to give a heterochiral crystal. Magnetic and differential scanning calorimetry (DSC studies were performed only for 1·AsF6, since the thermal stability in a high-temperature spin crossover (SCO region of 1·PF6 is poorer than that of 1·AsF6. 1·AsF6 shows an unsymmetrical hysteretic SCO between the low-spin–low-spin (LS–LS and high-spin–high-spin (HS–HS states at above room temperature. The critical temperatures of warming (Tc↑ and cooling (Tc↓ modes in the abrupt spin transition area are 485 and 401 K, respectively, indicating the occurrence of 84 K-wide thermal hysteresis in the first thermal cycle.

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.

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

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)

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)

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

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...

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)

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

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.

Nonanuclear Spin-Crossover Complex Containing Iron(II) and Iron(III) Based on a 2,6-Bis(pyrazol-1-yl)pyridine Ligand Functionalized with a Carboxylate Group.

Science.gov (United States)

Abhervé, Alexandre; Recio-Carretero, María José; López-Jordà, Maurici; Clemente-Juan, Juan Modesto; Canet-Ferrer, Josep; Cantarero, Andrés; Clemente-León, Miguel; Coronado, Eugenio

2016-09-19

The synthesis and magnetostructural characterization of [Fe(III)3(μ3-O)(H2O)3[Fe(II)(bppCOOH)(bppCOO)]6](ClO4)13·(CH3)2CO)6·(solvate) (2) are reported. This compound is obtained as a secondary product during synthesis of the mononuclear complex [Fe(II)(bppCOOH)2](ClO4)2 (1). The single-crystal X-ray diffraction structure of 2 shows that it contains the nonanuclear cluster of the formula [Fe(III)3(μ3-O)(H2O)3[Fe(II)(bppCOOH)(bppCOO)]6](13+), which is formed by a central Fe(III)3O core coordinated to six partially deprotonated [Fe(II)(bppCOOH)(bppCOO)](+) complexes. Raman spectroscopy studies on single crystals of 1 and 2 have been performed to elucidate the spin and oxidation states of iron in 2. These studies and magnetic characterization indicate that most of the iron(II) complexes of 2 remain in the low-spin (LS) state and present a gradual and incomplete spin crossover above 300 K. On the other hand, the Fe(III) trimer shows the expected antiferromagnetic behavior. From the structural point of view, 2 represents the first example in which bppCOO(-) acts as a bridging ligand, thus forming a polynuclear magnetic complex.

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)

Novel hydrogen storage materials: A review of lightweight complex hydrides

International Nuclear Information System (INIS)

Jain, I.P.; Jain, Pragya; Jain, Ankur

2010-01-01

The world is facing energy shortage and has become increasingly depending on new methods to store and convert energy for new, environmentally friendly methods of transportation and electrical energy generation as well as for portable electronics. Mobility - the transport of people and goods - is a socioeconomic reality that will surely increase in the coming years. Non-renewable fossil fuels are projected to decline sharply after 20-30 years. CO 2 emission from burning such fuels is the main cause for global warming. Currently whole world is seeking international commitment to cut emissions of greenhouse gases by 60% by 2050. Hydrogen which can be produced with little or no harmful emissions has been projected as a long term solution for a secure energy future. Increasing application of hydrogen energy is the only way forward to meet the objectives of Department of Energy (DOE), USA, i.e. reducing green house gases, increasing energy security and strengthening the developing countries economy. Any transition from a carbon-based/fossil fuel energy system to a hydrogen based economy involves overcoming significant scientific, technological and socio-economic barriers before ultimate implementation of hydrogen as the clean energy source of the future. Lot of research is going on in the world to find commercially viable solutions for hydrogen production, storage, and utilization, but hydrogen storage is very challenging, as application part of hydrogen energy totally depend on this. During early nineties and now also hydrogen storage as gas, liquid and metal hydride has been undertaken to solve the problem of hydrogen storage and transportation for the utilization as hydrogen energy, but none of these roots could became commercially viable along with the safety aspects for gas and liquid. With the result many new novel materials appeared involving different principles resulting in a fairly complex situation with no correlation between any two materials. In the present

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.

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

Directory of Open Access Journals (Sweden)

Luc Aymard

2015-08-01

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

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

Science.gov (United States)

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

2015-01-01

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

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

Li4FeH6: Iron-containing complex hydride with high gravimetric hydrogen density

Directory of Open Access Journals (Sweden)

Hiroyuki Saitoh

2014-07-01

Full Text Available Li4FeH6, which has the highest gravimetric hydrogen density of iron-containing complex hydrides reported so far, is synthesized by hydrogenation of a powder mixture of iron and LiH above 6.1 GPa at 900 °C. In situ synchrotron radiation X-ray diffraction measurements reveal that while kinetics require high temperature and thus high pressure for the synthesis, Li4FeH6 is expected to be thermodynamically stable slightly below room temperature at ambient pressure; further synthetic studies to suppress the kinetic effects may enable us to synthesize Li4FeH6 at moderate pressures. Li4FeH6 can be recovered at ambient conditions where Li4FeH6 is metastable.

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.

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)

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....

Reversible Heterolytic Cleavage of the H-H Bond by Molybdenum Complexes: Controlling the Dynamics of Exchange Between Proton and Hydride

Energy Technology Data Exchange (ETDEWEB)

Zhang, Shaoguang; Appel, Aaron M.; Bullock, R. Morris

2017-05-18

Controlling the heterolytic cleavage of the H-H bond of dihydrogen is critically important in catalytic hydrogenations and in the catalytic oxidation of H2. We show how the rate of reversible heterolytic cleavage of H2 can be controlled over nearly four orders of magnitude at 25 °C, from 2.1 × 103 s-1 to ≥107 s-1. Bifunctional Mo complexes, [CpMo(CO)(κ3-P2N2)]+ (P2N2 = 1,5-diaza-3,7-diphosphacyclooctane with alkyl/aryl groups on N and P), have been developed for heterolytic cleavage of H2 into a proton and a hydride, akin to Frustrated Lewis Pairs. The H-H bond cleavage is enabled by the basic amine in the second coordination sphere. The products of heterolytic cleavage of H2, Mo hydride complexes bearing protonated amines, [CpMo(H)(CO)(P2N2H)]+, were characterized by spectroscopic studies and by X-ray crystallography. Variable temperature 1H, 15N and 2-D 1H-1H ROESY NMR spectra indicated rapid exchange of the proton and hydride. The exchange rates are in the order [CpMo(H)(CO)(PPh2NPh2H)]+ > [CpMo(H)(CO)(PtBu2NPh2H)]+ > [CpMo(H)(CO)(PPh2NBn2H)]+ > [CpMo(H)(CO)(PtBu2NBn2H)]+ > [CpMo(H)(CO)(PtBu2NtBu2H)]+. The pKa values determined in acetonitrile range from 9.3 to 17.7, and show a linear correlation with the logarithm of the exchange rates. Thus the exchange dynamics are controlled through the relative acidity of the [CpMo(H)(CO)(P2N2H)]+ and [CpMo(H2)(CO)(P2N2)]+ isomers, providing a design principle for controlling heterolytic cleavage of H2.

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.

Synthesis, characterization, and reactivity of nickel hydride complexes containing 2,6-C6H3(CH2PR2)2 (R = tBu, cHex, and iPr) pincer ligands.

Science.gov (United States)

Boro, Brian J; Duesler, Eileen N; Goldberg, Karen I; Kemp, Richard A

2009-06-15

The syntheses and full characterization of nickel hydrides containing the PCP "pincer"-type ligand, where PCP = 2,6-C(6)H(3)(CH(2)PR(2))(2) (R = tBu, cHex, and iPr), are reported. These Ni-H complexes are prepared by the conversion of ((R)PCP)NiCl precursors into the corresponding nickel hydrides by use of appropriate hydride donors. Surprisingly, although the ((R)PCP)NiCl precursors are quite similar chemically, the conversions to the hydrides were not straightforward and required different hydride reagents to provide analytically pure products. While NaBH(4) was effective in the preparation of pure ((tBu)PCP)NiH, Super-Hydride solution (LiEt(3)BH in THF) was required to prepare either ((cHex)PCP)NiH or ((iPr)PCP)NiH. Attempts to prepare a Ni-H from ((Ph)PCP)NiCl with a variety of hydride reagents yielded only the free ligand as an identifiable product. Two of the derivatives, tBu and cHex, have also been subjected to single crystal X-ray analysis. The solid-state structures each showed a classic, near-square planar arrangement for Ni in which the PCP ligand occupied three meridional ligand points with the Ni-H trans to the Ni-C bond. The resulting Ni-H bond lengths were 1.42(3) and 1.55(2) A for the tBu and cHex derivatives, respectively.

Redox process catalysed by growing crystal-strengite, FePO4,2H2O, crystallizing from solution with iron(II) and hydroxylamine

Science.gov (United States)

Lundager Madsen, Hans Erik

2014-09-01

In an attempt to grow pure crystals of the iron(II) phosphate vivianite, Fe3(PO4)2,8H2O, from a solution of Mohr's salt, Fe(NH4)2(SO4)2,6H2O, added to a solution of ammonium phosphate, hydroxylammonium chloride, NH3OHCl, was added to the iron(II) stock solution to eliminate oxidation of iron(II) by oxygen from the air. However, the effect turned out to be the opposite of the expected: whereas hydroxylamine reduces iron(III) in bulk solution, it acted as a strong oxidant in the presence of growing iron phosphate crystals, causing the crystallization of the iron(III) phosphate strengite, FePO4,2H2O, as the only solid phase. Evidently the crystal surface catalyses oxidation of iron(II) by hydroxylamine. The usual composite kinetics of spiral growth and surface nucleation was found. The surface-nucleation part yielded edge free energy λ in the range 12-45 pJ/m, virtually independent of temperature and in the range typical for phosphates of divalent metals. The scatter of values for λ presumably arises from contributions from different crystal forms to the overall growth rate. The low mean value points to strong adsorption of iron(II), which is subsequently oxidized at the crystal surface, forming strengite. The state of the system did not tend to thermodynamic equilibrium, but to a metastable state, presumably controlled by the iron(II) rich surface layer of the crystal. In addition to crystal growth, it was possible to measure nucleation kinetics by light scattering (turbidimetry). A point of transition from heterogeneous to homogeneous nucleation was found, and from the results for the homogeneous domain a rather precise value of crystal surface free energy γ=55 mJ/m2 was found. This is a relatively low value as well, indicating that the redox process plays a role already at the nucleation stage.

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.

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,

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)

Investigation of the thermodynamics governing metal hydride synthesis in the molten state process

International Nuclear Information System (INIS)

Stowe, Ashley C.; Berseth, Polly A.; Farrell, Thomas P.; Laughlin, Laura; Anton, Donald; Zidan, Ragaiy

2008-01-01

This work is aimed at utilizing a new synthetic technique to form novel complex hydrides for hydrogen storage. This technique is based on fusing different complex hydrides at elevated temperatures and pressures to form new species with improved hydrogen storage properties. Under conditions of elevated hydrogen overpressures and temperatures the starting materials can reach melting or near-melting point without decomposing (molten state processing), allowing for enhanced diffusion and exchange of elements among the starting materials. The formation and stabilization of these compounds, using the molten state process, is driven by the thermodynamic and kinetic properties of the starting and resulting compounds. Complex hydrides (e.g. NaK 2 AlH 6 , Mg(AlH 4 ) 2 ) were formed, structurally characterized and their hydrogen desorption properties were tested. In this paper we report on investigations of the thermodynamic aspects governing the process and products. We also report on the role of molar ratio in determining the final products. The effectiveness of the molten state process is compared with chemomechanical synthetic methods (ball milling)

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.

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)

Characterization of a tricationic trigonal bipyramidal iron(IV) cyanide complex, with a very high reduction potential, and its iron(II) and iron(III) congeners.

Science.gov (United States)

England, Jason; Farquhar, Erik R; Guo, Yisong; Cranswick, Matthew A; Ray, Kallol; Münck, Eckard; Que, Lawrence

2011-04-04

Currently, there are only a handful of synthetic S = 2 oxoiron(IV) complexes. These serve as models for the high-spin (S = 2) oxoiron(IV) species that have been postulated, and confirmed in several cases, as key intermediates in the catalytic cycles of a variety of nonheme oxygen activating enzymes. The trigonal bipyramidal complex [Fe(IV)(O)(TMG(3)tren)](2+) (1) was both the first S = 2 oxoiron(IV) model complex to be generated in high yield and the first to be crystallographically characterized. In this study, we demonstrate that the TMG(3)tren ligand is also capable of supporting a tricationic cyanoiron(IV) unit, [Fe(IV)(CN)(TMG(3)tren)](3+) (4). This complex was generated by electrolytic oxidation of the high-spin (S = 2) iron(II) complex [Fe(II)(CN)(TMG(3)tren)](+) (2), via the S = 5/2 complex [Fe(III)(CN)(TMG(3)tren)](2+) (3), the progress of which was conveniently monitored by using UV-vis spectroscopy to follow the growth of bathochromically shifting ligand-to-metal charge transfer (LMCT) bands. A combination of X-ray absorption spectroscopy (XAS), Mössbauer and NMR spectroscopies was used to establish that 4 has a S = 0 iron(IV) center. Consistent with its diamagnetic iron(IV) ground state, extended X-ray absorption fine structure (EXAFS) analysis of 4 indicated a significant contraction of the iron-donor atom bond lengths, relative to those of the crystallographically characterized complexes 2 and 3. Notably, 4 has an Fe(IV/III) reduction potential of ∼1.4 V vs Fc(+/o), the highest value yet observed for a monoiron complex. The relatively high stability of 4 (t(1/2) in CD(3)CN solution containing 0.1 M KPF(6) at 25 °C ≈ 15 min), as reflected by its high-yield accumulation via slow bulk electrolysis and amenability to (13)C NMR at -40 °C, highlights the ability of the sterically protecting, highly basic peralkylguanidyl donors of the TMG(3)tren ligand to support highly charged high-valent complexes.

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.)

Experimental study of a metal hydride driven braided artificial pneumatic muscle

International Nuclear Information System (INIS)

Vanderhoff, Alexandra; Kim, Kwang J

2009-01-01

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 N Force /kg MH ) 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

Hybrid functional calculations of potential hydrogen storage material: Complex dimagnesium iron hydride

KAUST Repository

Ul Haq, Bakhtiar

2014-06-01

By employing the state of art first principles approaches, comprehensive investigations of a very promising hydrogen storage material, Mg 2FeH6 hydride, is presented. To expose its hydrogen storage capabilities, detailed structural, elastic, electronic, optical and dielectric aspects have been deeply analysed. The electronic band structure calculations demonstrate that Mg2FeH6 is semiconducting material. The obtained results of the optical bandgap (4.19 eV) also indicate that it is a transparent material for ultraviolet light, thus demonstrating its potential for optoelectronics application. The calculated elastic properties reveal that Mg2FeH6 is highly stiff and stable hydride. Finally, the calculated hydrogen (H2) storage capacity (5.47 wt.%) within a reasonable formation energy of -78 kJ mol-1, at room temperature, can be easily achievable, thus making Mg2FeH6 as potential material for practical H2 storage applications. Copyright © 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Reaction path sampling of the reaction between iron(II) and hydrogen peroxide in aqueous solution

NARCIS (Netherlands)

Ensing, B.; Baerends, E.J.

2002-01-01

Previously, we have studied the coordination and dissociation of hydrogen peroxide with iron(II) in aqueous solution by Car-Parrinello molecular dynamics at room temperature. We presented a few illustrative reaction events, in which the ferryl ion ([Fe(IV)O

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.)

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.)

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

Synthesis, X-ray and Mössbauer study of iron(II) complexes with trithiocyanuric acid (ttcH3). The X-ray structures of [Fe(bpy)3](ttcH) • 2bpy • 7H2O and [Fe(phen)3](ttcH2)(ClO4) • 2CH3OH • 2H2O

Czech Academy of Sciences Publication Activity Database

Kopel, P.; Trávníček, Zdeněk; Zbořil, R.; Mrozinski, J.

2004-01-01

Roč. 23, č. 14 (2004), s. 2193-2202 ISSN 0277-5387 R&D Projects: GA ČR(CZ) GA203/02/0436 Grant - others:GA MŠk1(CZ) MSM 153100007 Institutional research plan: CEZ:AV0Z5038910 Keywords : Iron(II) complexes * Trithiocyanuric acid * Mössbauer spectra * Crystal structures Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.586, year: 2004

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...

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.)

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.

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.

Phospholyl-uranium complexes

International Nuclear Information System (INIS)

Gradoz, Philippe

1993-01-01

After having reported a bibliographical study on penta-methylcyclopentadienyl uranium complexes, and a description of the synthesis and radioactivity of uranium (III) and (IV) boron hydrides compounds, this research thesis reports the study of mono and bis-tetramethyl-phospholyl uranium complexes comprising chloride, boron hydride, alkyl and alkoxide ligands. The third part reports the comparison of structures, stabilities and reactions of homologue complexes in penta-methylcyclopentadienyl and tetramethyl-phospholyl series. The last part addresses the synthesis of tris-phospholyl uranium (III) and (IV) complexes. [fr

An extremely bulky tris(pyrazolyl)methanide: a tridentate ligand for the synthesis of heteroleptic magnesium(II) and ytterbium(II) alkyl, hydride, and iodide complexes.

Science.gov (United States)

Lalrempuia, Ralte; Stasch, Andreas; Jones, Cameron

2015-02-01

The tris(pyrazolyl)methane compound HC(3-Ad-5-Mepz)3 [1, 3-Ad-5-Mepz=3-(1-adamantyl)-5-methylpyrazolyl] and its regioisomer, HC(3-Ad-5-Mepz)2 (3-Me-5-Adpz), were synthesized and crystallographically characterized. Deprotonation of 1 with MeLi afforded the lithium complex [{κ(3) -N-C(3-Ad-5-Mepz)3 }Li(thf)], which incorporates a tris(pyrazolyl)methanide ligand of unprecedented bulk. Reaction of 1 with MeMgI gave the ionic coordination complex [{κ(3) -N-HC(3-Ad-5-Mepz)3 }MgMe]I, which was readily deprotonated to afford the neutral compound [{κ(3) -N-C(3-Ad-5-Mepz)3 }MgMe]. The related magnesium butyl compound [{κ(3) -N-C(3-Ad-5-Mepz)3 }MgBu] was prepared from the reaction of 1 and MgBu2 . Treating this with LiAlH4 or LiAlD4 led to rare examples of terminal magnesium hydride/deuteride complexes, [{κ(3) -N-C(3-Ad-5-Mepz)3 }MgH/D]. All neutral magnesium alkyl and hydride compounds were crystallographically authenticated. Reaction of [{κ(3) κN-C(3-Ad-5-Mepz)3 }Li(thf)] with [YbI2 (thf)2 ] yielded the first structurally characterized f-block tris(pyrazolyl)methanide complex, [{κ(3) -N-C(3-Ad-5-Mepz)3 }YbI(thf)]. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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)

Direct synthesis of magnetite nanoparticles from iron(II) carboxymethylcellulose and their performance as NMR contrast agents

Energy Technology Data Exchange (ETDEWEB)

Gomes da Silva, Delmarcio; Hiroshi Toma, Sergio; Menegatti de Melo, Fernando [Instituto de Química, Universidade de São Paulo, São Paulo, SP (Brazil); Carvalho, Larissa Vieira C.; Magalhães, Alvicler; Sabadini, Edvaldo [Instituto de Química, Universidade Estadual de Campinas – UNICAMP, Campinas, SP (Brazil); Domingues dos Santos, Antônio [Instituto de Física, Universidade de São Paulo, São Paulo, SP (Brazil); Araki, Koiti [Instituto de Química, Universidade de São Paulo, São Paulo, SP (Brazil); Toma, Henrique E., E-mail: henetoma@iq.usp.br [Instituto de Química, Universidade de São Paulo, São Paulo, SP (Brazil)

2016-01-01

Iron(II) carboxymethylcellulose (CMC) has been successfully employed in the synthesis of hydrophylic magnetite nanoparticles stabilized with a biopolymer coating, aiming applications in NMR imaging. The new method encompasses a convenient one-step synthetic procedure, allowing a good size control and yielding particles of about 10 nm (core size). In addition to the biocompatibility, the nanoparticles have promoted a drastic reduction in the transverse relaxation time (T{sub 2}) of the water protons. The relaxivity rates have been investigated as a function of the nanoparticles concentration, showing a better performance in relation to the common NMR contrast agents available in the market. - Highlights: • Stable, hydrophylic magnetic nanoparticles have been obtained. • Direct use of iron(II) carboxymethylcellulose improves the synthesis. • The magnetic nanoparticles exhibit high spin–spin relaxivity. • The particles promote dark contrast by decreasing the T{sub 2} relaxation time.

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

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.

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...

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

Synthesis and catalytic activity of N-heterocyclic silylene (NHSi) cobalt hydride for Kumada coupling reactions.

Science.gov (United States)

Qi, Xinghao; Sun, Hongjian; Li, Xiaoyan; Fuhr, Olaf; Fenske, Dieter

2018-02-20

The electron-rich silylene Co(i) chloride 5 was obtained through the reaction of CoCl(PMe 3 ) 3 with chlorosilylene. Complex 5 reacted with 1,3-siladiazole HSiMe(NCH 2 PPh 2 ) 2 C 6 H 4 to give the silylene Co(iii) hydride 6 through chelate-assisted Si-H activation. To the best of our knowledge, complex 6 is the first example of Co(iii) hydride supported by N-heterocyclic silylene. Complexes 5 and 6 were fully characterized by spectroscopic methods and X-ray diffraction analysis. Complex 6 was used as an efficient precatalyst for Kumada cross-coupling reactions. Compared with the related complex 3 supported by only trimethylphosphine, complex 6 as a catalyst supported by both chlorosilylene and trimethylphosphine exhibits a more efficient performance for the Kumada cross-coupling reactions. A novel catalytic radical mechanism was suggested and experimentally verified. As an intermediate silylene cobalt(ii) chloride 6d was isolated and structurally characterized.

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)

Immobilized Tannin from Sanseviera trifasciata on Carbon as Adsorbent For Iron(II in Polluted Water Source

Directory of Open Access Journals (Sweden)

Irfan Hanafi Arif

2016-03-01

Full Text Available The organic-agricultural waste resulted from local farmer or community gardening recently paid public attention. The presence and easily grown of “Lidah Mertua” or Sanseviera trifasciata being focused on potency investigation for its prospecting application. It was reported contain some phenolic and also tannin extracted from aqueous solvents. This paper revealed recent investigation applying of its isolated tannin from leave part to modifying of activated carbon. The previous report published that carbon were able to adsorb some toxic heavy metals. However, it has some limitation including lower capacity adsorption. Impregnated or immobilized the tannin-isolated from S. trifasciata leaves was able to modify the carbon functionality, physical appearance, pores size, and it adsorption capacity. Both Langmuir and Freundlich adsorption mechanism model also disclosed the developed adsorbent mechanism of iron(II adsorption on the adsorbent tannin-immobolized on carbon. The real test using community well drilling water source also gave important finding on the concentration of iron(II contained on water source.

Synthesis and reactions of imines of α,β-ethylenic silicon-containing aldehydes with complex metal hydrides

International Nuclear Information System (INIS)

Surnin, V.A.; Stadnichuk, M.D.

1986-01-01

Imines of 3-trimethylsilyl-2-propenal or its hydrocarbon analog are reduced chemoselectively at the C=N double bond by sodium borohydride. The direction of lithium aluminum hydride reduction of these imines is not influenced by the nature of the element attached to the C=C bond silicon versus carbon, but rather is determined by the nature of the radical group attached to the nitrogen atom; N-arylimines undergo addition with lithium aluminum hydride at the C=N bond exclusively, whereas for N-alkylimines the addition reactions occur either partially or in full in the 1,4-position, depending on the reaction conditions, to give imines of saturated aldehydes after demetallation

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.)

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

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

Effect of Phosphorylation and Copper(II or Iron(II Ions Enrichment on Some Physicochemical Properties of Spelt Starch

Directory of Open Access Journals (Sweden)

Jacek Rożnowski

Full Text Available ABSTRACT: This paper provides an assessment of the effect of saturation of spelt starch and monostarch phosphate with copper or iron ions on selected physicochemical properties of the resulting modified starches. Native and modified spelt starch samples were analyzed for selected mineral element content using Atomic Absorption Spectroscopy (AAS. Thermodynamic properties were measured using DSC, and pasting properties by RVA. Flow curves of 5% pastes were plotted and described using the Herschel-Bulkley model. The structure recovery ratio was measured. AAS analysis established the presence of iron(II and copper(II ions in the samples of modified starches and that potassium and magnesium ions had leached from them. In comparison to unfortified samples, enriching native starch with copper(II ions decreases value of all temperatures of phase transformation about 1.3-2.7 °C, but in case of monostarch phosphates bigger changes (2.8-3.7 °C were observed. Fortified native spelt starch with copper(II ions caused increasing the final viscosity of paste from 362 to 429 mPa·s. However, presence iron(II ions in samples caused reduced its final viscosity by 170 (spelt starch and 103 mPa·s (monostarch phosphate. Furthermore, enriching monostarch phosphate contributed to reduce degree of structure recovery of pastes from 70.9% to 66.6% in case of copper(II ions and to 59.9% in case of iron(II ions.

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

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

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

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)

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.

Gallium hydride complexes stabilised by multidentate alkoxide ligands: precursors to thin films of Ga2O3 at low temperatures.

Science.gov (United States)

Pugh, David; Bloor, Leanne G; Parkin, Ivan P; Carmalt, Claire J

2012-05-07

The donor-functionalised alkoxides {Me(3-x)N(CH(2)CH(2)O)(x)} (L(x); x = 1, 2) have been used to form gallium hydride complexes [{GaH(2)(L(1))}(2)] and [{GaH(L(2))}(2)] that are stable and isolable at room temperature. Along with a heteroleptic gallium tris(alkoxide) complex [Ga(L(1))(3)] and the dimeric complex [{GaMe(L(2))}(2)], these compounds have been used as single-source precursors for the deposition of Ga(2)O(3) by aerosol-assisted chemical vapour deposition (AACVD) with toluene as solvent. The resulting films were mostly transparent, indicating low levels of carbon contamination, and they were also mainly amorphous. However, [Ga(L(1))(3)] did contain visibly crystalline material deposited at a substrate temperature of 450 °C, by far the lowest ever observed for the CVD of gallium oxide. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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)

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.)

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.

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

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.

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.

CO Reduction to CH3OSiMe3: Electrophile-Promoted Hydride Migration at a Single Fe Site.

Science.gov (United States)

Deegan, Meaghan M; Peters, Jonas C

2017-02-22

One of the major challenges associated with developing molecular Fischer-Tropsch catalysts is the design of systems that promote the formation of C-H bonds from H 2 and CO while also facilitating the release of the resulting CO-derived organic products. To this end, we describe the synthesis of reduced iron-hydride/carbonyl complexes that enable an electrophile-promoted hydride migration process, resulting in the reduction of coordinated CO to a siloxymethyl (L n Fe-CH 2 OSiMe 3 ) group. Intramolecular hydride-to-CO migrations are extremely rare, and to our knowledge the system described herein is the first example where such a process can be accessed from a thermally stable M(CO)(H) complex. Further addition of H 2 to L n Fe-CH 2 OSiMe 3 releases CH 3 OSiMe 3 , demonstrating net four-electron reduction of CO to CH 3 OSiMe 3 at a single Fe site.

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)

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

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

Complexation Effect on Redox Potential of Iron(III)-Iron(II) Couple: A Simple Potentiometric Experiment

Science.gov (United States)

Rizvi, Masood Ahmad; Syed, Raashid Maqsood; Khan, Badruddin

2011-01-01

A titration curve with multiple inflection points results when a mixture of two or more reducing agents with sufficiently different reduction potentials are titrated. In this experiment iron(II) complexes are combined into a mixture of reducing agents and are oxidized to the corresponding iron(III) complexes. As all of the complexes involve the…

Linear Dimerization of Terminal Alkynes by Bis( tetramethylphenylcyclopentadienyl) Titanium-Magnesium Hydride and Acetylide Complexes

Czech Academy of Sciences Publication Activity Database

Mach, Karel; Gyepes, R.; Horáček, Michal; Petrusová, Lidmila; Kubišta, Jiří

2003-01-01

Roč. 68, č. 10 (2003), s. 1877-1896 ISSN 0010-0765 R&D Projects: GA ČR GA203/02/0774; GA ČR GA203/02/0436 Institutional research plan: CEZ:AV0Z4040901 Keywords : titanium * alkynes * hydrides Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.041, year: 2003

Chemical Hydride Slurry for Hydrogen Production and Storage

Energy Technology Data Exchange (ETDEWEB)

McClaine, Andrew W

2008-09-30

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

Rational Design in Catalysis: A Mechanistic Study of β-Hydride Eliminations in Gold(I) and Gold(III) Complexes Based on Features of the Reaction Valley.

Science.gov (United States)

Castiñeira Reis, Marta; López, Carlos Silva; Kraka, Elfi; Cremer, Dieter; Faza, Olalla Nieto

2016-09-06

β-Hydride eliminations for ethylgold(III) dichloride complexes are identified as reactions with an unusually long prechemical stage corresponding to the conformational preparation of the reaction complex and spanning six phases. The prechemical process is characterized by a geared rotation of the L-Au-L group (L = Cl) driving methyl group rotation and causing a repositioning of the ligands. This requires more than 28 kcal/mol of the total barrier of 34.0 kcal/mol, according to the unified reaction valley approach, which also determines that the energy requirements of the actual chemical process leading to the β-elimination product are only about 5.5 kcal/mol. A detailed mechanistic analysis was used as a basis for a rational design of substrates (via substituents on the ethyl group) and/or ligands, which can significantly reduce the reaction barrier. This strategy takes advantage of either a higher trans activity of the ligands or a tuned electronic demand of the ethyl group. The β-hydride elimination of gold(I) was found to suffer from strong Coulomb and exchange repulsion when a positively charged hydrogen atom enforces a coordination position in a d(10)-configured gold atom, thus triggering an unassisted σ-π Au(I)-C conversion.

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.)

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.)

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...

Update: An efficient synthesis of poly(ethylene glycol)-supported iron(II) porphyrin using a click reaction and its application for the catalytic olefination of aldehydes

KAUST Repository

Chinnusamy, Tamilselvi R.

2012-05-09

The facile synthesis of polyethylene glycol (PEG)-immobilized iron(II) porphyrin using a copper-catalyzed azide-alkyne [3+2] cycloaddition "click" reaction is reported. The prepared complex 5 (PEG-C 51H 39FeN 7O) was found to be an efficient catalyst for the selective olefination of aldehydes with ethyl diazoacetate in the presence of triphenylphosphine, and afforded excellent olefin yields with high (E) selectivities. The PEG-supported catalyst 5 was readily recovered by precipitation and filtration, and was recycled through ten runs without significant activity loss. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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)

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.

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

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.)

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.

The influence of surface morphology and oxide microstructure on the nucleation and growth of uranium hydride on alpha uranium

International Nuclear Information System (INIS)

Hanrahan, R.J. Jr.; Hawley, M.E.; Brown, G.W.

1998-01-01

While the bulk kinetics of the uranium-hydrogen reaction are well understood, the mechanisms underlying the initial nucleation of uranium hydride on uranium remain controversial. In this study, the authors have employed environmental cell optical microscopy, Scanning Electron Microscopy (SEM) and Atomic Force Microscopy, (AFM) in an attempt to relate the structure of the surface and the microstructure of the substrate with the susceptibility and site of hydride nucleation. Samples have been investigated with varying grain size, inclusion (carbide) concentration, and thermal history. There is a clear correlation to heat treatment immediately prior to hydrogen exposure. Susceptibility to hydride formation also appears to be related to impurities in the uranium. The oxidized surface is very complex, exhibiting wide variations in thickness and topography between samples, between grains in the same sample, and within individual grains. It is, however, very difficult to relate this fine scale variability to the relatively sparse hydride initiation sites. Therefore, the surface oxide layer itself does not appear to control the sites where hydride attack is initiated, although it must play a role in the induction period prior to hydride initiation

The influence of surface morphology and oxide microstructure on the nucleation and growth of uranium hydride on alpha uranium

Energy Technology Data Exchange (ETDEWEB)

Hanrahan, R.J. Jr.; Hawley, M.E.; Brown, G.W. [Los Alamos National Lab., NM (United States). Materials Science and Technology Div.

1998-12-31

While the bulk kinetics of the uranium-hydrogen reaction are well understood, the mechanisms underlying the initial nucleation of uranium hydride on uranium remain controversial. In this study the authors have employed environmental cell optical microscopy, Scanning Electron Microscopy (SEM) and Atomic Force Microscopy, (AFM) in an attempt to relate the structure of the surface and the microstructure of the substrate with the susceptibility and site of hydride nucleation. Samples have been investigated with varying grain size, inclusion (carbide) concentration, and thermal history. There is a clear correlation to heat treatment immediately prior to hydrogen exposure. Susceptibility to hydride formation also appears to be related to impurities in the uranium. The oxidized surface is very complex, exhibiting wide variations in thickness and topography between samples, between grains in the same sample, and within individual grains. It is, however, very difficult to relate this fine scale variability to the relatively sparse hydride initiation sites. Therefore, the surface oxide layer itself does not appear to control the sites where hydride attack is initiated, although it must play a role in the induction period prior to hydride initiation.

The influence of surface morphology and oxide microstructure on the nucleation and growth of uranium hydride on alpha uranium

Energy Technology Data Exchange (ETDEWEB)

Hanrahan, R.J. Jr.; Hawley, M.E.; Brown, G.W.

1998-12-31

While the bulk kinetics of the uranium-hydrogen reaction are well understood, the mechanisms underlying the initial nucleation of uranium hydride on uranium remain controversial. In this study, the authors have employed environmental cell optical microscopy, Scanning Electron Microscopy (SEM) and Atomic Force Microscopy, (AFM) in an attempt to relate the structure of the surface and the microstructure of the substrate with the susceptibility and site of hydride nucleation. Samples have been investigated with varying grain size, inclusion (carbide) concentration, and thermal history. There is a clear correlation to heat treatment immediately prior to hydrogen exposure. Susceptibility to hydride formation also appears to be related to impurities in the uranium. The oxidized surface is very complex, exhibiting wide variations in thickness and topography between samples, between grains in the same sample, and within individual grains. It is, however, very difficult to relate this fine scale variability to the relatively sparse hydride initiation sites. Therefore, the surface oxide layer itself does not appear to control the sites where hydride attack is initiated, although it must play a role in the induction period prior to hydride initiation.

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

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

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.

Calculation of vibrational spectra of complex hydrides, LiBeH/sub 3/, NaBeH/sub 3/ and LiMgH/sub 3/

Energy Technology Data Exchange (ETDEWEB)

Sukhanov, L P; Boldyrev, A I [AN SSSR, Chernogolovka. Inst. Novykh Khimicheskikh Problem

1984-03-01

The non-empirical Hartree-Fock-Ruthan method with a two-exponent Ros-Zigban basis has been used to calculate the coefficients of harmonic force field, frequency and intensity of normal vibrations of the LiBeH/sub 3/, NaBeH/sub 3/ and LiMgH/sub 3/ complex hydrides. Attribution of vibrational types is conducted. Isotope shifts for different isotope substitutions in the L(MH/sub 3/) are calculated. The effect of the nature of both the outer-spherical cation L/sup +/ and central atom M on the vibrational spectrum is discussed.

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%.

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

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.

Nuclear fuel technology - Determination of uranium in solutions, uranium hexafluoride and solids - Part 2: Iron(II) reduction/cerium(IV) oxidation titrimetric method

International Nuclear Information System (INIS)

2004-01-01

This first edition of ISO 7097-1 together with ISO 7097-2:2004 cancels and replaces ISO 7097:1983, which has been technically revised, and ISO 9989:1996. ISO 7097 consists of the following parts, under the general title Nuclear fuel technology - Determination of uranium in solutions, uranium hexafluoride and solids: Part 1: Iron(II) reduction/potassium dichromate oxidation titrimetric method; Part 2: Iron(II) reduction/cerium(IV) oxidation titrimetric method. This part 2. of ISO 7097 describes procedures for determination of uranium in solutions, uranium hexafluoride and solids. The procedures described in the two independent parts of this International Standard are similar: this part uses a titration with cerium(IV) and ISO 7097-1 uses a titration with potassium dichromate

Nuclear fuel technology - Determination of uranium in solutions, uranium hexafluoride and solids - Part 1: Iron(II) reduction/potassium dichromate oxidation titrimetric method

International Nuclear Information System (INIS)

2004-01-01

This first edition of ISO 7097-1 together with ISO 7097-2:2004 cancels and replaces ISO 7097:1983, which has been technically revised, and ISO 9989:1996. ISO 7097 consists of the following parts, under the general title Nuclear fuel technology - Determination of uranium in solutions, uranium hexafluoride and solids: Part 1: Iron(II) reduction/potassium dichromate oxidation titrimetric method; Part 2: Iron(II) reduction/cerium(IV) oxidation titrimetric method. This part 1. of ISO 7097 describes procedures for the determination of uranium in solutions, uranium hexafluoride and solids. The procedures described in the two independent parts of this International Standard are similar: this part uses a titration with potassium dichromate and ISO 7097-2 uses a titration with cerium(IV)

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.

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.

Oxygen reduction reaction at MWCNT-modified nanoscale iron(II) tetrasulfophthalocyanine: remarkable performance over platinum and tolerance toward methanol in alkaline medium

CSIR Research Space (South Africa)

Fashedemi, OO

2015-04-01

Full Text Available A nanoscale iron(II) tetrasulfophthalocyanine (nanoFeTSPc) catalyst obtained by co-ordinating with hexadecyltrimethylammonium bromide and subsequently anchored onto multi-walled carbon nanotubes (MWCNTs) for oxygen reduction reaction (ORR) has been...

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.

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.

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

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)

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)

Group 13 β-ketoiminate compounds: gallium hydride derivatives as molecular precursors to thin films of Ga2O3.

Science.gov (United States)

Pugh, David; Marchand, Peter; Parkin, Ivan P; Carmalt, Claire J

2012-06-04

Bis(β-ketoimine) ligands, [R{N(H)C(Me)-CHC(Me)═O}(2)] (L(1)H(2), R = (CH(2))(2); L(2)H(2), R = (CH(2))(3)), linked by ethylene (L(1)) and propylene (L(2)) bridges have been used to form aluminum, gallium, and indium chloride complexes [Al(L(1))Cl] (3), [Ga(L(n))Cl] (4, n = 1; 6, n = 2) and [In(L(n))Cl] (5, n = 1; 7, n = 2). Ligand L(1) has also been used to form a gallium hydride derivative [Ga(L(1))H] (8), but indium analogues could not be made. β-ketoimine ligands, [Me(2)N(CH(2))(3)N(H)C(R')-CHC(R')═O] (L(3)H, R' = Me; L(4)H, R' = Ph), with a donor-functionalized Lewis base have also been synthesized and used to form gallium and indium alkyl complexes, [Ga(L(3))Me(2)] (9) and [In(L(3))Me(2)] (10), which were isolated as oils. The related gallium hydride complexes, [Ga(L(n))H(2)] (11, n = 3; 12, n = 4), were also prepared, but again no indium hydride species could be made. The complexes were characterized mainly by NMR spectroscopy, mass spectrometry, and single crystal X-ray diffraction. The β-ketoiminate gallium hydride compounds (8 and 11) have been used as single-source precursors for the deposition of Ga(2)O(3) by aerosol-assisted (AA)CVD with toluene as the solvent. The quality of the films varied according to the precursor used, with the complex [Ga(L(1))H] (8) giving by far the best quality films. Although the films were amorphous as deposited, they could be annealed at 1000 °C to form crystalline Ga(2)O(3). The films were analyzed by powder XRD, SEM, and EDX.

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)

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)

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)

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

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)

Iodometric determination of peroxydiphosphate in the presence of copper(II) or iron(II) as catalyst.

Science.gov (United States)

Kapoor, S; Sharma, P D; Gupta, Y K

1975-09-01

Peroxydiphosphate can be determined iodometrically in the presence of a large excess of potassium iodide with copper(II) or iron(II) as catalyst through the operation of the Cu(II)/Cu(I) or Fe(II)/Fe(III) cycle. The method is applicable in HClO(4), H(2)SO(4), HCl and CH(3)COOH acid media in the range 0.1-1.0M studied. Nickel, manganese(II), cobalt(II), silver, chloride and phosphate are without effect.

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.

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

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....

Recent advances in improving performances of the lightweight complex hydrides Li-Mg-N-H system

Directory of Open Access Journals (Sweden)

Bao Zhang

2017-02-01

Full Text Available A brief review of state-of-the art advances in improving performances of the lightweight complex hydrides Li-Mg-N-H system is reported. Among the hydrogen storage materials, Li-Mg-N-H combination systems are regarded as one of the most potential candidates for the vehicular applications owing to their high hydrogen storage capacity (>5 wt% H and a more appropriate thermodynamic properties of hydrogen absorption and desorption. In the Li-Mg-N-H systems, tremendous efforts have been devoted to improving the hydrogen storage properties by adjusting composition, revealing reaction mechanisms, adding catalysts and refining the microstructures, etc. During the studies, different mechanisms, such as the coordinated two-molecule or multimolecule reaction mechanism and the ammonia-mediated mechanism, are proposed and applied under some certain conditions. Catalysis and nanosizing are very effective in enhancing the kinetic properties and thermodynamic destabilization of Li-Mg-N-H systems. Due to nano effects, the space-confinement and nanoconfinement seems to be more effective for improving the hydrogen storage performance, and it is great significant to develop hydrogen storage materials by studying the nanoconfined effects on the Li-Mg-N-H systems.

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.

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

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.

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

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.

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.

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

Optimization and comprehensive characterization of metal hydride based hydrogen storage systems using in-situ Neutron Radiography

Science.gov (United States)

Börries, S.; Metz, O.; Pranzas, P. K.; Bellosta von Colbe, J. M.; Bücherl, T.; Dornheim, M.; Klassen, T.; Schreyer, A.

2016-10-01

For the storage of hydrogen, complex metal hydrides are considered as highly promising with respect to capacity, reversibility and safety. The optimization of corresponding storage tanks demands a precise and time-resolved investigation of the hydrogen distribution in scaled-up metal hydride beds. In this study it is shown that in situ fission Neutron Radiography provides unique insights into the spatial distribution of hydrogen even for scaled-up compacts and therewith enables a direct study of hydrogen storage tanks. A technique is introduced for the precise quantification of both time-resolved data and a priori material distribution, allowing inter alia for an optimization of compacts manufacturing process. For the first time, several macroscopic fields are combined which elucidates the great potential of Neutron Imaging for investigations of metal hydrides by going further than solely 'imaging' the system: A combination of in-situ Neutron Radiography, IR-Thermography and thermodynamic quantities can reveal the interdependency of different driving forces for a scaled-up sodium alanate pellet by means of a multi-correlation analysis. A decisive and time-resolved, complex influence of material packing density is derived. The results of this study enable a variety of new investigation possibilities that provide essential information on the optimization of future hydrogen storage tanks.

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

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

Fatigue crack initiation at complex flaws in hydrided Zr-2.5%Nb samples from CANDU pressure tubes

International Nuclear Information System (INIS)

Stoica, L.; Radu, V.

2016-01-01

The paper addresses the phenomena which occur at locations where the oxide layer of the inner surface of CANDU tube pressure is damaged by the contact with the fuel element or due to the action of hard particles at the interface between the tube pressure and bearing pad of fuel element. In such situations generate defects, which most often are defects known as ''bearing pad fretting flaws'' or ''debris fretting flaws''. In this paper the experiments are completed in a series of previous works on the mechanical fatigue phenomenon on samples prepared from the pressure tube Zr-2.5% Nb alloy. The phenomenon of variable mechanical stress (or fatigue) may lead to initiation of cracks at the tip of volumetric flaws, according to the accumulation of hydrides, which then fractures and can propagate through the tube wall pressure due to the mechanism of type DHC (Delayed Hydride Cracking). (authors)

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.

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

Binding of molecular oxygen by an artificial heme analogue: investigation on the formation of an Fe–tetracarbene superoxo complex

KAUST Repository

Anneser, Markus R.; Haslinger, Stefan; Pö thig, Alexander; Cokoja, Mirza; D'Elia, Valerio; Hö gerl, Manuel P.; Basset, Jean-Marie; Kü hn, Fritz E.

2016-01-01

The dioxygen reactivity of a cyclic iron(II) tetra–NHC-complex (NHC: N-heterocyclic carbene) is investigated. Divergent oxidation behavior is observed depending on the choice of the solvent (acetonitrile or acetone). In the first case, exposure

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.

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

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.

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)

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

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.

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%

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

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.

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.

Graphitic nanofibres as catalyst for improving the dehydrogenation behavior of complex aluminium hydrides

Energy Technology Data Exchange (ETDEWEB)

Hudson, M. Sterlin Leo; Raghubanshi, Himanshu; Pukazhselvan, D.; Srivastava, O.N. [Banaras Hindu Univ., Varnasi (India). Hydrogen Energy Center

2010-07-01

In the present work, we explored the catalytic effect of graphitic nanofibres (GNF) particularly of two different morphology, namely planar graphitic nanofibre (PGNF) and helical graphitic nanofibre (HGNF) for enhancement of hydrogen desorption from complex aluminium hydrides such as LiAlH{sub 4} and LiMg(AlH{sub 4}){sub 3}. We found that the catalytic activity of fibres depends mainly on its morphology. Hence helical morphology fibres possess superior catalytic activity than planar graphitic nanofibres. The desorption temperature for 8 mol% HGNF admixed LiAlH{sub 4} gets lowered from 159 C to 128 C with significantly faster kinetics. In 8 mol% HGNF admixed LiMg(AlH{sub 4}){sub 3} sample, the desorption temperature gets lowered from 105 C to {proportional_to}70 C. The activation energy calculated for the first step decomposition of LiAlH{sub 4} admixed with 8 mol% HGNF is {proportional_to}68 kJmol{sup -1}, whereas that for pristine LiAlH{sub 4} it is 107 kJ/mol. The activation energy calculated for as synthesized LiMg(AlH{sub 4}){sub 3} is {proportional_to}66 kJ/mol. Since the first step decomposition of LiMg(AlH{sub 4}){sub 3} occurs during GNF admixing, the activation energy for initial step decomposition of GNF admixed LiMg(AlH{sub 4}){sub 3} could not be estimated. (orig.)

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.)

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

The preparation of magnetite from iron(III) and iron(II) salt solutions

International Nuclear Information System (INIS)

Segal, D.L.

1980-10-01

Methods are described for the preparation of magnetite from iron(III) and iron(II) salt solutions at temperatures between 295 to 373 K. The effect of the reagent concentration, a chelating agent and different alkali-metal cations on the formation of magnetite has been investigated. The magnetite samples have been examined by X-ray diffraction, transmission electron microscopy, adsorption of nitrogen, emission spectroscopy, X-ray photoelectron spectroscopy and by determination of the point of zero charge. A review of previous work on the preparation of magnetite in an aqueous environment is also included. This work is relevant to the corrosion processes which can occur in the water coolant circuits of nuclear reactors. (author)

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)

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)

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

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.

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.

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.

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

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

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.

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

Energy Technology Data Exchange (ETDEWEB)

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

2011-02-14

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

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

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.

Synthesis and reactivity of triscyclopentadienyl uranium (III) and (IV) complexes

International Nuclear Information System (INIS)

Berthet, J.C.

1992-01-01

The reactions of (RC 5 H 4 ) 3 U with R=trimethylsilylcyclopentadienyl or tertiobutylcyclopentadienyl are studied for the synthesis of new uranium organometallic compounds. Reactions with sodium hydride are first described uranium (III) anionic hydrides obtained are oxidized for synthesis of stable uranium (IV) organometallic hydrides. Stability of these compounds is discussed. Reactivity of these uranium (III) and (IV) hydrides are studied. Formation of new binuclear compounds with strong U-O and U-N bonds is examined and crystal structure are presented. Monocyclooctatetraenylic uranium complexes are also investigated

Electrochemical characterization of mixed self-assembled films of water-soluble single-walled carbon nanotube-poly(m-aminobenzene sulfonic acid) and Iron(II) tetrasulfophthalocyanine

CSIR Research Space (South Africa)

Agboola, BO

2010-09-01

Full Text Available The redox activities of water-soluble iron(II) tetrasulfophthalocyanine (FeTSPc) and single-walled carbon nanotube-poly(m-aminobenzene sulfonic acid) (SWCNT-PABS) adsorbed on a gold surface precoated with a self-assembled monolayer (SAM) of 2...

Bis(2,3,5,6-tetra-2-pyridylpyrazine-κ3N2,N1,N6iron(II bis(dicyanamidate 4.5-hydrate

Directory of Open Access Journals (Sweden)

R. Cortés

2010-03-01

Full Text Available In the title compound, [Fe(C24H16N62][N(CN2]2·4.5H2O, the central iron(II ion is hexacoordinated by six N atoms of two tridentate 2,3,5,6-tetra-2-pyridylpyrazine (tppz ligands. Two dicyanamide anions [dca or N(CN2−] act as counter-ions, and 4.5 water molecules act as solvation agents. The structure contains isolated cationic iron(II–tppz complexes and the final neutrality is obtained with the two dicyanamide anions. One of the dicyanamide anions and a water molecule are disordered with an occupancy ratio of 0.614 (8:0.386 (8. O—H...O, O—H...N and C—H...O hydrogen bonds involving dca, water and tppz molecules are observed.

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.

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

Quantum-chemical study of structure and stability of hydride complexes Li4BeH6 and Li4MgH6

International Nuclear Information System (INIS)

Zyubin, A.S.; Charkin, O.P.; Klabo, D.A.; Shlojfer, P.R.

1993-01-01

Nonempirical calculations of geometrical structure, electronic structure and relative energies of a wide range of different configurations of Li 4 MH 6 (M = Be, Mg) molecules were conducted in order to predict the existence of complex hydrides with high hydrogen content. It was revealed, that Li 4 MH 6 molecules were stable to decomposition and could exist in isolated state or in inert matrices. Li 4 MH 6 systems are noted for existence of several isomers with energy, close to the basic structure. The presence of M atoms with coordination number (CN) equal to four is considered to be their common feature. The structure, where CN of Be and Mg is equal to three, are less stable. Configurations, including M atoms with CN = 5 or 6, are much more unfavorable from the viewpoint of energy

Accommodation stresses in hydride precipitates by synchrotron x-ray diffraction

International Nuclear Information System (INIS)

Santisteban, J R; Vicente, M A; Vizcaino, P; Banchik, A D; Almer, J

2012-01-01

Hydride-forming materials (Zr, Ti, Nb, etc) are affected by a sub-critical crack growth mechanism that involves the diffusion of H to the stressed region ahead of a crack, followed by nucleation and fracture of hydrides at the crack tip [1]. The phenomenon is intermittent, with the crack propagating through the hydride and stopping when it reaches the matrix. By repeating these processes, the crack propagates through a component at a rate that is highly dependent on the temperature history of the component. Most research effort to understand this phenomenon has occurred within the nuclear industry, as it affects the safe operation of pressure tubes (Zr2.5%Nb) and the long-term storage of nuclear fuel (Zircaloy cladding). Stress-induced hydride formation is a consequence of the volume dilatation that accompanies hydride formation (of the order of 15%), which is elastoplastically accommodated by the matrix and precipitate. Compressive stresses are expected within hydride precipitates due to the constraint imposed by the matrix. Such 'accommodation' stresses are essential ingredients in all theoretical models developed to assess the crack growth rate dependence on operational variables such as temperature, applied stress intensity factor, or overall H concentration [2]. Yet little experimental information is available about the magnitude and directionality of such accommodation stresses. Synchrotron X-ray diffraction is the only technique capable of quantifying such stresses. Here we briefly describe the fundaments of the technique, when used through an area detector placed in transmission geometry. The results of the experiments have allowed us to produce a comprehensive picture about the magnitude and origin of accommodation stresses in δ zirconium hydride platelets (author)

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

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.

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.

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)

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)

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.

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)

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.

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

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)

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)

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

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.

Metal Hydrides for Rechargeable Batteries

Energy Technology Data Exchange (ETDEWEB)

Valoeen, Lars Ole

2000-03-01

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

Light induced electron transfer reactions of metal complexes

International Nuclear Information System (INIS)

Sutin, N.; Creutz, C.

1980-01-01

Properties of the excited states of tris(2,2'-bipyridine) and tris(1,10-phenanthroline) complexes of chromium(III), iron(II), ruthenium(II), osmium(II), rhodium(III), and iridium(III) are described. The electron transfer reactions of the ground and excited states are discussed and interpreted in terms of the driving force for the reaction and the distortions of the excited states relative to the corresponding ground states. General considerations relevant to the conversion of light into chemical energy are presented and progress in the use of polypyridine complexes to effect the light decomposition of water into hydrogen and oxygen is reviewed

Characteristics of hydride precipitation and reorientation in spent-fuel cladding

International Nuclear Information System (INIS)

Chung, H. M.; Strain, R. V.; Billone, M. C.

2000-01-01

The morphology, number density, orientation, distribution, and crystallographic aspects of Zr hydrides in Zircaloy fuel cladding play important roles in fuel performance during all phases before and after discharge from the reactor, i.e., during normal operation, transient and accident situations in the reactor, temporary storage in a dry cask, and permanent storage in a waste repository. In the past, partly because of experimental difficulties, hydriding behavior in irradiated fuel cladding has been investigated mostly by optical microscopy (OM). In the present study, fundamental metallurgical and crystallographic characteristics of hydride precipitation and reorientation were investigated on the microscopic level by combined techniques of OM and transmission electron and scanning electron microscopy (TEM and SEM) of spent-fuel claddings discharged from several boiling and pressurized water reactors (BWRs and PWRs). Defueled sections of standard and Zr-lined Zircaloy-2 fuel claddings, irradiated to fluences of ∼3.3 x 10 21 n cm -2 and ∼9.2 x 10 21 n cm -2 (E > 1 MeV), respectively, were obtained from spent fuel rods discharged from two BWRs. Sections of standard and low-tin Zircaloy-4 claddings, irradiated to fluences of ∼4.4 x 10 21 n cm -2 , ∼5.9 x 10 21 n cm -2 , and ∼9.6 x 10 21 n cm -2 (E > 1 MeV) in three PWRs, were also obtained. Microstructural characteristics of hydrides were analyzed in as-irradiated condition and after gas-pressurization-burst or expanding-mandrel tests at 292-325 C in Ar for some of the spent-fuel claddings. Analyses were also conducted of hydride habit plane, morphology, and reorientation characteristics on unirradiated Zircaloy-4 cladding that contained dense radial hydrides. Reoriented hydrides in the slowly cooled unirradiated cladding were produced by expanding-mandrel loading

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

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

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.

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.

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.

Hydrogen transmission/storage with a metal hydride/organic slurry

Energy Technology Data Exchange (ETDEWEB)

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

1998-08-01

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

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.)

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

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.

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)

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.

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)

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

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

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

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.)

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

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

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.)

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.

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.

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.

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

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.

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.

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).

Spectrophotometric Determination of Iron(II and Cobalt(II by Direct, Derivative, and Simultaneous Methods Using 2-Hydroxy-1-Naphthaldehyde-p-Hydroxybenzoichydrazone

Directory of Open Access Journals (Sweden)

V. S. Anusuya Devi

2012-01-01

Full Text Available Optimized and validated spectrophotometric methods have been proposed for the determination of iron and cobalt individually and simultaneously. 2-hydroxy-1-naphthaldehyde-p-hydroxybenzoichydrazone (HNAHBH reacts with iron(II and cobalt(II to form reddish-brown and yellow-coloured [Fe(II-HNAHBH] and [Co(II-HNAHBH] complexes, respectively. The maximum absorbance of these complexes was found at 405 nm and 425 nm, respectively. For [Fe(II-HNAHBH], Beer’s law is obeyed over the concentration range of 0.055–1.373 μg mL−1 with a detection limit of 0.095 μg mL−1 and molar absorptivity ɛ, 5.6 × 104 L mol−1 cm−1. [Co(II-HNAHBH] complex obeys Beer’s law in 0.118–3.534 μg mL−1 range with a detection limit of 0.04 μg mL−1 and molar absorptivity, ɛ of 2.3 × 104 L mol−1 cm−1. Highly sensitive and selective first-, second- and third-order derivative methods are described for the determination of iron and cobalt. A simultaneous second-order derivative spectrophotometric method is proposed for the determination of these metals. All the proposed methods are successfully employed in the analysis of various biological, water, and alloy samples for the determination of iron and cobalt content.

Structural and magnetic transformations in NdMn2Hx hydrides

International Nuclear Information System (INIS)

Budziak, A.; Zachariasz, P.; Pełka, R.; Figiel, H.; Żukrowski, J.; Woch, M.W.

2012-01-01

Highlights: ► Full structural phase diagram is presented for the NdMn 2 H x (2.0 ≤ x ≤ 4.0) hydrides in the temperature range of 70–385 K. ► For samples x = 2.0, 2.5, and 4.0 a splitting into two phases with different hydrogen concentrations are observed. ► Only for samples with x = 3.0 and 3.5 no spinodal decompositions are detected. ► The effects of hydrogen absorption on structural properties are shown to be reflected in magnetic behavior. ► A huge jump of magnetic ordering temperatures from ∼104 K for host NdMn 2 to above 200 K for its hydrides is observed or anticipated. - Abstract: X-ray powder diffraction and bulk magnetization measurements were used to study structural and magnetic properties of hydrides NdMn 2 H x (2.0 ≤ x ≤ 4.0). The X-ray investigations performed in the temperature range 70–385 K have revealed many structural transformations at low temperatures. In particular, a transformation from the hexagonal to the monoclinic phase and spinodal decompositions were observed. The magnetic behavior of the hydrides is correlated with the structural transitions. A tentative structural diagram is presented. The obtained results are compared with the properties of other cubic and hexagonal RMn 2 H x hydrides.

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

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.

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

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)

Diverse roles of hydrogen in rhenium carbonyl chemistry: hydrides, dihydrogen complexes, and a formyl derivative.

Science.gov (United States)

Li, Nan; Xie, Yaoming; King, R Bruce; Schaefer, Henry F

2010-11-04

Rhenium carbonyl hydride chemistry dates back to the 1959 synthesis of HRe(CO)₅ by Hieber and Braun. The binuclear H₂Re₂(CO)₈ was subsequently synthesized as a stable compound with a central Re₂(μ-H)₂ unit analogous to the B₂(μ-H)₂ unit in diborane. The complete series of HRe(CO)(n) (n = 5, 4, 3) and H₂Re₂(CO)(n) (n = 9, 8, 7, 6) derivatives have now been investigated by density functional theory. In contrast to the corresponding manganese derivatives, all of the triplet rhenium structures are found to lie at relatively high energies compared with the corresponding singlet structures consistent with the higher ligand field splitting of rhenium relative to manganese. The lowest energy HRe(CO)₅ structure is the expected octahedral structure. Low-energy structures for HRe(CO)(n) (n = 4, 3) are singlet structures derived from the octahedral HRe(CO)₅ structure by removal of one or two carbonyl groups. For H₂Re₂(CO)₉ a structure HRe₂(CO)₉(μ-H), with one terminal and one bridging hydrogen atom, lies within 3 kcal/mol of the structure Re₂(CO)₉(η²-H₂), similar to that of Re₂(CO)₁₀. For H₂Re₂(CO)(n) (n = 8, 7, 6) the only low-energy structures are doubly bridged singlet Re₂(μ-H)₂(CO)(n) structures. Higher energy dihydrogen complex structures are also found.

Moessbauer spectroscopic characterization of macromolecule-metallochlorophyll complexes

International Nuclear Information System (INIS)

Inoue, H.; Fukuda, K.; Nonomura, Y.; Fluck, E.

1993-01-01

The bis-adducts of iron chlorophylls with poly(4-vinylpyridine-costyrene) (PVP) have been prepared and characterized by 57 Fe Moessbauer spectroscopy. The Moessbauer parameters of the PVP-adducts of iron chlorophylls are typical of low-spin iron(II) complexes. The central iron(III) ion is spontaneously reduced upon the axial coordination of PVP to iron(III) chlorophylls. The general tendency in the spontaneous reduction of the iron(III) chlorophylls has been interpreted in terms of the σ-donor and π-acceptor power of the axial macromolecular ligand. (orig.)

Reversible Li-insertion in nanoscaffolds: A promising strategy to alter the hydrogen sorption properties of Li-based complex hydrides

NARCIS (Netherlands)

Ngene, Peter; Verkuijlen, Margriet H. W.; Barre, Charlotte; Kentgens, Arno P. M.; de Jongh, Petra E.

Intercalation and de-intercalation of lithium into graphene layers is a well-established phenomenon in Li-ion battery technology. Here we show how this phenomenon can be exploited to destabilize, and alter the hydrogen sorption behaviour of Li-based metal hydrides (LiBH4 and LiAlH4), thereby

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

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

Effect of hydriding temperature and strain rate on the ductile-brittle transition in β treated Zircaloy-4

International Nuclear Information System (INIS)

Bai, J.B.

1996-01-01

In this paper, the effect of hydriding temperature and strain rate on the ductile-brittle transition in β treated Zircaloy-4 has been investigated. The hydriding temperature used is 700degC, strain rates being 4x10 -4 s -1 and 4x10 -3 s -1 . The results show that at same conditions the ductility of hydrides decreases as the hydriding temperature decreases. There exists a critical temperature (transition temperature) of 250degC for hydriding at 700degC, below which the hydrided specimens (and so for the hydrides) are brittle, while above it they are ductile. This transition temperature is lower than the one mentioned by various authors obtained for hydriding at 400degC. For the same hydriding temperature of 700degC, the specimens tested at 4x10 -3 s -1 are less ductile than those tested at 4x10 -4 s -1 . Furthermore, unlike at a strain rate of 4x10 -4 s -1 , there is no more a clear ductile-brittle transition behaviour. (author)

Saline-water bioleaching of chalcopyrite with thermophilic, iron(II)- and sulfur-oxidizing microorganisms.

Science.gov (United States)

Watling, Helen R; Collinson, David M; Corbett, Melissa K; Shiers, Denis W; Kaksonen, Anna H; Watkin, Elizabeth L J

2016-09-01

The application of thermoacidophiles for chalcopyrite (CuFeS2) bioleaching in hot, acidic, saline solution was investigated as a possible process route for rapid Cu extraction. The study comprised a discussion of protective mechanisms employed for the survival and/or adaptation of thermoacidophiles to osmotic stress, a compilation of chloride tolerances for three genera of thermoacidophiles applied in bioleaching and an experimental study of the activities of three species in a saline bioleaching system. The data showed that the oxidation rates of iron(II) and reduced inorganic sulfur compounds (tetrathionate) were reduced in the presence of chloride levels well below chloride concentrations in seawater, limiting the applicability of these microorganisms in the bioleaching of CuFeS2 in saline water. Copyright © 2016. Published by Elsevier Masson SAS.

In vitro studies on interactions of iron salts and complexes with food-stuffs and medicaments.

Science.gov (United States)

Geisser, P

1990-07-01

It has been shown in the present study that food components such as phytic acid, oxalic acid, tannin, sodium alginate, choline and choline salts, vitamins A, D3 and E, soy oil and soy flour, do not undergo any interactions with iron(III)-hydroxide polymaltose complex (Ferrum Hausmann). Phytic acid, oxalic acid, tannin and sodium alginate, however, react with iron(II) or iron(III)-salts at pH values of 3.0, 5.5 and 8.0, giving rise to iron complexes. Trimethylamine-N-oxide, which is present in fish meal, reacts with iron(II)-sulphate to produce iron(III) reaction products; it does not react with iron(III)-hydroxide polymaltose complex. Special soybean flours show no irreversible adsorption or precipitation with iron(III)-hydroxyide polymaltose complex over the pH range 3.0-8.0, in contrast to iron(II)-sulphate. Antacids containing aluminium hydroxide, talc, ion exchange resins or other unabsorbable, insoluble components absorb iron(III)-hydroxide polymaltose complex in the pH range 3.0-8.0 in a reversible manner, while the strong adsorption or precipitation observed with iron(II)-sulphate at pH 8.0 is irreversible. No interaction was observed between the steroid hormones studied and iron(II)-sulphate or iron(III)-hydroxide polymaltose complex. On the basis of the measured compatibilities, iron(III)-hydroxide polymaltose complex can be administered orally simultaneously with many other drugs, without prejudicing the absorption of iron or of the other drug as is often seen with iron(II) and iron(III) salts.

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)

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.

New Transition metal assisted complex borohydrides for hydrogen storage

International Nuclear Information System (INIS)

Sesha Srinivasan; Elias Lee Stefanakos; Yogi Goswami

2006-01-01

High capacity hydrogen storage systems are indeed essential for the on-board vehicular application that leads to the pollution free environment. Apart from the various hydrogen storage systems explored in the past, complex hydrides involving light weight alkali/alkaline metals exhibits promising hydrogenation/ dehydrogenation characteristics. New transition metal assisted complex borohydrides [Zn(BH 4 ) 2 ] have been successfully synthesized by an inexpensive mechano-chemical process. These complex hydrides possesses gravimetric hydrogen storage capacity of ∼8.4 wt.% at around 120 C. We have determined the volumetric hydrogen absorption and desorption of these materials for a number of cycles. Another complex borohydride mixture LiBH 4 /MgH 2 catalyzed with ZnCl 2 has been synthesized and characterized using various analytical techniques. (authors)

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.)

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.

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)

Influence of hydrides orientation on strain, damage and failure of hydrided zircaloy-4; Influence de l'orientation des hydrures sur les modes de deformation, d'endommagement et de rupture du zircaloy-4 hydrure

Energy Technology Data Exchange (ETDEWEB)

Racine, A

2005-09-15

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

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

Science.gov (United States)

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

2017-04-01

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

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.

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.

Effect of Gaseous Impurities on Long-Term Thermal Cycling and Aging Properties of Complex Hydrides for Hydrogen Storage

Energy Technology Data Exchange (ETDEWEB)

Chandra, Dhanesh [Primary Contact; Lamb, Joshua; Chien, Wen-Ming; Talekar, Anjali; and Pal, Narendra

2011-03-28

This program was dedicated to understanding the effect of impurities on Long-Term Thermal Cycling and aging properties of Complex Hydrides for Hydrogen Storage. At the start of the program we found reversibility between Li2NH+LiH LiH+LiNH2 (yielding ~5.8 wt.%H capacity). Then we tested the effect of impurity in H2 gas by pressure cycling at 255°C; first with industrial gas containing ppm levels of O2 and H2O as major impurities. Both these impurities had a significant impact on the reversibility and decreased the capacity by 2.65 wt.%H. Further increase in number of cycles from 500 to 1100 showed only a 0.2 wt%H more weight loss, showing some capacity is still maintained after a significant number of cycles. The loss of capacity is attributed to the formation of ~55 wt% LiH and ~30% Li2O, as major contaminant phases, along with the hydride Li2NH phase; suggesting loss of nitrogen during cycling. The effect of 100 ppm H2O in H2 also showed a decrease of ~2.5 wt.%H (after 560 cycles), and 100ppm O2 in H2; a loss of ~4.1 wt.%. Methane impurity (100 ppm, 100cycles), showed a very small capacity loss of 0.9 wt.%H under similar conditions. However, when Li3N was pressure cycled with 100ppmN2-H2 there were beneficial effects were observed (255oC); the reversible capacity increased to 8.4wt.%H after 853 cycles. Furthermore, with 20 mol.%N2-H2 capacity increased to ~10 wt.%H after 516 cycles. We attribute this enhancement to the reaction of nitrogen with liquid lithium during cycling as the Gibbs free energy of formation of Li3N (Go = -98.7 kJ/mol) is more negative than that of LiH (Go = -50.3 kJ/mol). We propose that the mitigation of hydrogen capacity losses is due to the destabilization of the LiH phase that tends to accumulate during cycling. Also more Li2NH phase was found in the cycled product. Mixed Alanates (3LiNH2:Li3AlH6) showed that 7 wt% hydrogen desorbed under dynamic vacuum. Equilibrium experiments (maximum 12 bar H2) showed up to 4wt% hydrogen reversibly

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.

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.

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)

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

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.

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

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)

Large-scale synthesis of high-purity well-aligned carbon nanotubes using pyrolysis of iron(II) phthalocyanine and acetylene

Science.gov (United States)

Liu, B. C.; Lee, T. J.; Lee, S. H.; Park, C. Y.; Lee, C. J.

2003-08-01

Well-aligned carbon nanotubes (CNTs) with high purity have been produced by pyrolysis of iron(II) phthalocyanine and acetylene at 800 °C. The synthesized CNTs have a length of 75 μm and diameters ranging from 20 to 60 nm. The CNTs have a bamboo-like structure and exhibit good crystallinity of graphite sheets. The growth rate of the CNTs was rapidly increased with adding C 2H 2. Our results demonstrate that the proposed growth method is suitable to large-scale synthesis of high-purity well-aligned CNTs on various substrates.

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.

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

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

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...

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

Energy Technology Data Exchange (ETDEWEB)

Auer, Henry; Guehne, Robin; Bertmer, Marko; Weber, Sebastian; Wenderoth, Patrick; Hansen, Thomas Christian; Haase, Jürgen; Kohlmann, Holger (Leipzig); (Saarland-MED); (ILL)

2017-01-18

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

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)

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)

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.

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.)

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-11-14

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

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

KAUST Repository

Solá ns, Xavier Luis; Chow, Catherine; Gouré , Eric; Kaya, Yasemin; Basset, Jean-Marie; Taoufik, Mostafa; Quadrelli, Elsje Alessandra; Eisenstein, Odile

2012-01-01

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

Characterization of a U-Mo alloy subjected to direct hydriding of the gamma phase

International Nuclear Information System (INIS)

Balart, Silvia N.; Bruzzoni, Pablo; Granovsky, Marta S.

2003-01-01

The Reduced Enrichment for Research and Test Reactors (RERTR) program has imposed the need to develop plate-type fuel elements based on high density uranium compounds, such as U-Mo alloys. One of the steps in the fabrication of the fuel elements is the pulverization of the fissile material. In the case of the U-Mo alloys, the pulverization can be accomplished through hydriding - dehydriding. Two alternative methods of the hydriding-dehydriding process, namely the selective hydriding in alpha phase (HS-alpha) and the massive hydriding in gamma phase (HM-gamma) are currently being studied at the Comision Nacional de Energia Atomica. The HM-gamma method was reproduced at laboratory scale starting from a U-7 wt % Mo alloy. The hydrided and dehydrided materials were characterized using metallographic techniques, scanning electron microscopy, energy dispersive X-ray analysis and X-ray diffraction. These results are compared with previous results of the HS-alpha method. (author)

Mechanistic aspects of dinitrogen cleavage and hydrogenation to produce ammonia in catalysis and organometallic chemistry: relevance of metal hydride bonds and dihydrogen.

Science.gov (United States)

Jia, Hong-Peng; Quadrelli, Elsje Alessandra

2014-01-21

Dinitrogen cleavage and hydrogenation by transition-metal centers to produce ammonia is central in industry and in Nature. After an introductory section on the thermodynamic and kinetic challenges linked to N2 splitting, this tutorial review discusses three major classes of transition-metal systems (homogeneous, heterogeneous and biological) capable of achieving dissociation and hydrogenation of dinitrogen. Molecular complexes, solid-state Haber-Bosch catalytic systems, silica-supported tantalum hydrides and nitrogenase will be discussed. Emphasis is focused on the reaction mechanisms operating in the process of dissociation and hydrogenation of dinitrogen, and in particular on the key role played by metal hydride bonds and by dihydrogen in such reactions.

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

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...

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.

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.

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

International Nuclear Information System (INIS)

Barreiro, M M; Grana, D R; Kokubu, G A; Luppo, M I; Mintzer, S; Vigna, G

2010-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2010-04-15

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

Influence of temperature and hydrogen content on stress-induced radial hydride precipitation in Zircaloy-4 cladding

Energy Technology Data Exchange (ETDEWEB)

Desquines, J., E-mail: jean.desquines@irsn.fr; Drouan, D.; Billone, M.; Puls, M.P.; March, P.; Fourgeaud, S.; Getrey, C.; Elbaz, V.; Philippe, M.

2014-10-15

Radial hydride precipitation in stress relieved Zircaloy-4 fuel claddings is studied using a new thermal–mechanical test. Two maximum temperatures for radial hydride precipitation heat treatment are studied, 350 and 450 °C with hydrogen contents ranging between 50 and 600 wppm. The new test provides two main results of interest: the minimum hoop stress required to precipitate radial hydrides and a maximum stress above which, all hydrides precipitate in the radial direction. Based on these two extreme stress conditions, a model is derived to determine the stress level required to obtain a given fraction of radial hydrides after high temperature thermal–mechanical heat treatment. The proposed model is validated using metallographic observation data on pressurized tubes cooled down under constant pressure. Most of the samples with reoriented hydrides are further subjected to a ductility test. Using finite element modeling, the test results are analyzed in terms of crack nucleation within radial hydrides at the outer diameter and crack growth through the thickness of the tubular samples. The combination of test results shows that samples with hydrogen contents of about 100 wppm had the lowest ductility.

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.

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

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

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.

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)

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.

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

Conceptual study on HTGR-IS hydrogen supply system using organic hydrides

International Nuclear Information System (INIS)

Terada, Atsuhiko; Noguchi, Hiroki; Takegami, Hiroaki; Kamiji, Yu; Inagaki, Yoshiyuki

2012-02-01

We have proposed a hydrogen supply-chain system, which is a storage/supply system of large amount of hydrogen produced by HTGR-IS hydrogen production system. The organic chemical hydride method is one of the candidate techniques in the system for hydrogen storage and transportation. In this study, properties of organic hydrides and conventional hydrogen storage/supply system were surveyed to make use of the conceptual design of the hydrogen supply system using an organic hydrides method with VHTR-IS hydrogen production process (hydrogen production: 85,400 Nm 3 /h). Conceptual specifications of the main equipments were designed for the hydrogen supply system consisting of hydrogenation and dehydrogenation process. It was also clarified the problems of hydrogen supply system, such as energy efficiency and system optimization. (author)

Metal interferences and their removal prior to the determination of As(T) and As(III) in acid mine waters by hydride generation atomic absorption spectrometry

Science.gov (United States)

McCleskey, R. Blaine; Nordstrom, D. Kirk; Ball, James W.

2003-01-01

Hydride generation atomic absorption spectrometry (HGAAS) is a sensitive and selective method for the determination of total arsenic (arsenic(III) plus arsenic(V)) and arsenic(III); however, it is subject to metal interferences for acid mine waters. Sodium borohydride is used to produce arsine gas, but high metal concentrations can suppress arsine production. This report investigates interferences of sixteen metal species including aluminum, antimony(III), antimony(V), cadmium, chromium(III), chromium(IV), cobalt, copper(II), iron(III), iron(II), lead, manganese, nickel, selenium(IV), selenium(VI), and zinc ranging in concentration from 0 to 1,000 milligrams per liter and offers a method for removing interfering metal cations with cation exchange resin. The degree of interference for each metal without cation-exchange on the determination of total arsenic and arsenic(III) was evaluated by spiking synthetic samples containing arsenic(III) and arsenic(V) with the potential interfering metal. Total arsenic recoveries ranged from 92 to 102 percent for all metals tested except antimony(III) and antimony(V) which suppressed arsine formation when the antimony(III)/total arsenic molar ratio exceeded 4 or the antimony(V)/total arsenic molar ratio exceeded 2. Arsenic(III) recoveries for samples spiked with aluminum, chromium(III), cobalt, iron(II), lead, manganese, nickel, selenium(VI), and zinc ranged from 84 to 107 percent over the entire concentration range tested. Low arsenic(III) recoveries occurred when the molar ratios of metals to arsenic(III) were copper greater than 120, iron(III) greater than 70, chromium(VI) greater than 2, cadmium greater than 800, antimony(III) greater than 3, antimony(V) greater than 12, or selenium(IV) greater than 1. Low recoveries result when interfering metals compete for available sodium borohydride, causing incomplete arsine production, or when the interfering metal oxidizes arsenic(III). Separation of interfering metal cations using

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.

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.

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)

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

Recently, Kim proposed a new DHC model where a driving force for the DHC is a supersaturated hydrogen concentration as a result of a hysteresis of the terminal solid solubility (TSS) of hydrogen in zirconium alloys upon a heating and a cooling. This model was demonstrated to be valid through a model experiment where the prior plastic deformation facilitated nucleation of the reoriented hydrides, thus reducing the supersaturated hydrogen concentration at the plastic zone ahead of the crack tip and causing hydrogen to move to the crack tip from the bulk region. Thus, an approach to the test temperature by a cooling is required to create a supersaturation of hydrogen, which is a driving force for the DHC of zirconium alloys. However, despite the absence of the supersaturation of hydrogen due to an approach to the test temperature by a heating, DHC is observed to occur in zirconium alloys at the test temperatures below 180 .deg. C. As to this DHC phenomenon, Kim proposed that stress-induced transformation from γ-hydrides to δ-hydrides is likely to be a cause of this, based on Root's observation that the γ-hydride is a stable phase at temperatures lower than 180 .deg. C. In other words, the hydrides formed at the crack tip would be δ-hydrides due to the stressinduced transformation while the bulk region still maintains the initial hydride phase or γ-hydrides. It should be noted that Ambler has also assumed the crack tip hydrides to be δ-hydrides. When the δ-hydrides or ZrH1.66 are precipitated at the crack tip due to the transformation of the γ-hydrides or ZrH, the crack tip will have a decreased concentration of dissolved hydrogen in zirconium, considering the atomic ratio of hydrogen and zirconium in the γ- and δ-hydrides. In contrast, due to no stress-induced transformation of hydrides, the bulk region maintains the initial concentration of dissolved hydrogen. Hence, there develops a difference in the hydrogen concentration or .C between the bulk and the

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

Recently, Kim proposed a new DHC model where a driving force for the DHC is a supersaturated hydrogen concentration as a result of a hysteresis of the terminal solid solubility (TSS) of hydrogen in zirconium alloys upon a heating and a cooling. This model was demonstrated to be valid through a model experiment where the prior plastic deformation facilitated nucleation of the reoriented hydrides, thus reducing the supersaturated hydrogen concentration at the plastic zone ahead of the crack tip and causing hydrogen to move to the crack tip from the bulk region. Thus, an approach to the test temperature by a cooling is required to create a supersaturation of hydrogen, which is a driving force for the DHC of zirconium alloys. However, despite the absence of the supersaturation of hydrogen due to an approach to the test temperature by a heating, DHC is observed to occur in zirconium alloys at the test temperatures below 180 .deg. C. As to this DHC phenomenon, Kim proposed that stress-induced transformation from {gamma}-hydrides to {delta}-hydrides is likely to be a cause of this, based on Root's observation that the {gamma}-hydride is a stable phase at temperatures lower than 180 .deg. C. In other words, the hydrides formed at the crack tip would be {delta}-hydrides due to the stressinduced transformation while the bulk region still maintains the initial hydride phase or {gamma}-hydrides. It should be noted that Ambler has also assumed the crack tip hydrides to be {delta}-hydrides. When the {delta}-hydrides or ZrH1.66 are precipitated at the crack tip due to the transformation of the {gamma}-hydrides or ZrH, the crack tip will have a decreased concentration of dissolved hydrogen in zirconium, considering the atomic ratio of hydrogen and zirconium in the {gamma}- and {delta}-hydrides. In contrast, due to no stress-induced transformation of hydrides, the bulk region maintains the initial concentration of dissolved hydrogen. Hence, there develops a difference in the

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

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.

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.

Development of low angle grain boundaries in lightly deformed superconducting niobium and their influence on hydride distribution and flux perturbation

Science.gov (United States)

Sung, Z.-H.; Wang, M.; Polyanskii, A. A.; Santosh, C.; Balachandran, S.; Compton, C.; Larbalestier, D. C.; Bieler, T. R.; Lee, P. J.

2017-05-01

This study shows that low angle grain boundaries (LAGBs) can be created by small 5% strains in high purity (residual resistivity ratio ≥ 200) superconducting radio frequency (SRF)-grade single crystalline niobium (Nb) and that these boundaries act as hydrogen traps as indicated by the distribution of niobium hydrides (Nb1-xHx). Nb1-xHx is detrimental to SRF Nb cavities due to its normal conducting properties at cavity operating temperatures. By designing a single crystal tensile sample extracted from a large grain (>5 cm) Nb ingot slice for preferred slip on one slip plane, LAGBs and dense dislocation boundaries developed. With chemical surface treatments following standard SRF cavity fabrication practice, Nb1-xHx phases were densely precipitated at the LAGBs upon cryogenic cooling (8-10 K/min). Micro-crystallographic analysis confirmed heterogeneous hydride precipitation, which included significant hydrogen atom accumulation in LAGBs. Magneto-optical imaging analysis showed that these sites can then act as sites for both premature flux penetration and eventually flux trapping. However, this hydrogen related degradation at LAGBs did not completely disappear even after an 800 °C/2 h anneal typically used for hydrogen removal in SRF Nb cavities. These findings suggest that hydride precipitation at an LAGB is facilitated by a non-equilibrium concentration of vacancy-hydrogen (H) complexes aided by mechanical deformation and the hydride phase interferes with the recovery process under 800 °C annealing.

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}).

High-efficiency heat pump technology using metal hydrides (eco-energy city project)

Energy Technology Data Exchange (ETDEWEB)

Morita, Y.; Harada, T.; Niikura, J.; Yamamoto, Y.; Suzuki, J. [Human Environmental Systems Development Center, Matsushita Electric Industrial Co., Ltd., Moriguchi, Osaka (Japan); Gamo, T. [Corporate Environmental Affairs Div., Matsushita Electric Industrial Co., Ltd., Kadoma, Osaka (Japan)

1999-07-01

Metal hybrides are effective materials for utilizing hydrogen as a clean energy medium. That is, when the metal hydrides absorb or desorb the hydrogen, a large heat output of reaction occurs. So, the metal hydrides can be applied to a heat pump. We have researched on a high efficiency heat pump technology using their metal hydrides. In this report, a double effect type metal hydride heat pump configuration is described in which the waste heat of 160 C is recovered in a factory cite and transported to areas far distant from the industrial district. In the heat recovery unit, a low pressure hydrogen is converted into highly effective high pressure hydrogen by applying the metal hydrides. Other metal hydrides perform the parts of heating by absorbing the hydrogen and cooling by desorbing the hydrogen in the heat supply unit. One unit scale of the system is 3 kW class as the sum of heating and cooling. This system using the hydrogen absorbing alloy also has good energy storage characteristics and ambient hydrogen pressure self-safety control ability. Furthermore, this heating and cooling heat supply system is not harmful to the natural environment because it is a chlorofluorocarbon-free, and low noise type system. We have developed in the following element technologies to attain the above purposes, that is development of hydrogen absorbing alloys with high heat outputs and technologies to construct the heat pump system. This study is proceeded at present as one of the programs in New Sunshine Project, which aims for development of ingenious energy utilization technology to achieve reduction of primary energy consumption with keeping cultural and wealthy life and preventing deterioration of global environment. (orig.)

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

Pulsed laser deposition of air-sensitive hydride epitaxial thin films: LiH

Energy Technology Data Exchange (ETDEWEB)

Oguchi, Hiroyuki, E-mail: oguchi@nanosys.mech.tohoku.ac.jp [Department of Nanomechanics, Tohoku University, Sendai 980-8579 (Japan); Micro System Integration Center (muSIC), Tohoku University, Sendai 980-0845 (Japan); Isobe, Shigehito [Creative Research Institution, Hokkaido University, Sapporo 001-0021 (Japan); Graduate School of Engineering, Hokkaido University, Sapporo 060-8628 (Japan); Kuwano, Hiroki [Department of Nanomechanics, Tohoku University, Sendai 980-8579 (Japan); Shiraki, Susumu; Hitosugi, Taro [Advanced Institute for Materials Research (AIMR), Tohoku University, Sendai 980-8577 (Japan); Orimo, Shin-ichi [Advanced Institute for Materials Research (AIMR), Tohoku University, Sendai 980-8577 (Japan); Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan)

2015-09-01

We report on the epitaxial thin film growth of an air-sensitive hydride, lithium hydride (LiH), using pulsed laser deposition (PLD). We first synthesized a dense LiH target, which is key for PLD growth of high-quality hydride films. Then, we obtained epitaxial thin films of [100]-oriented LiH on a MgO(100) substrate at 250 °C under a hydrogen pressure of 1.3 × 10{sup −2} Pa. Atomic force microscopy revealed that the film demonstrates a Stranski-Krastanov growth mode and that the film with a thickness of ∼10 nm has a good surface flatness, with root-mean-square roughness R{sub RMS} of ∼0.4 nm.

Pulsed laser deposition of air-sensitive hydride epitaxial thin films: LiH

International Nuclear Information System (INIS)

Oguchi, Hiroyuki; Isobe, Shigehito; Kuwano, Hiroki; Shiraki, Susumu; Hitosugi, Taro; Orimo, Shin-ichi

2015-01-01

We report on the epitaxial thin film growth of an air-sensitive hydride, lithium hydride (LiH), using pulsed laser deposition (PLD). We first synthesized a dense LiH target, which is key for PLD growth of high-quality hydride films. Then, we obtained epitaxial thin films of [100]-oriented LiH on a MgO(100) substrate at 250 °C under a hydrogen pressure of 1.3 × 10 −2 Pa. Atomic force microscopy revealed that the film demonstrates a Stranski-Krastanov growth mode and that the film with a thickness of ∼10 nm has a good surface flatness, with root-mean-square roughness R RMS of ∼0.4 nm

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)

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

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.

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

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

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

International Nuclear Information System (INIS)

Cui, J.; Shek, G.K.; Wang, Z.R.

2007-01-01

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

Combined effects of radiation damage and hydrides on the ductility of Zircaloy-2

International Nuclear Information System (INIS)

Wisner, S.B.; Adamson, R.B.

1998-01-01

Interest remains high regarding the effects of zirconium hydride precipitates on the ductility of reactor Zircaloy components, particularly in irradiated material. Previous studies have reported that ductility reductions are much greater at room temperature compared to reactor component temperatures. It is often concluded that the effects of irradiation dominate the ductility reduction observed in test specimens, although there is no consensus as to whether hydriding effects are additive. Many of the tests reported in the literature are difficult to interpret due to variations in test specimen geometry and material history. In this paper, we present the results of an experimental program aimed at clearly describing the combined effects of irradiation and hydriding on ductility parameters under conditions of a realistic test specimen design and well characterized hydride content, distribution and orientation. Experiments were conducted at 295 and 605 K, respectively on Zircaloy-2 tubing segments containing 10-800 ppm hydrogen and neutron fluences between 0.9 x 10 25 nm -2 (E>1 MeV). Tests utilized the well proven localized ductility specimen which applies plane strain tension in the hoop direction of the tubing segment. In all cases, hydrides were also oriented in the hoop or circumferential direction and were uniformly distributed across the tubing wall. Results indicate that at 605 K, the ductility of irradiated material was almost independent of hydride content, retaining above 4% uniform elongation and 25% reduction in an area for the highest fluences and hydrogen contents. Even at 295 K, measurable ductility was retained for irradiated material with up to 600 ppm hydrogen. In the paper, results of fractographic analyses and strain rate are also discussed

δ-hydride habit plane determination in α-zirconium by strain energy minimization technique at 25 and 300 deg C

International Nuclear Information System (INIS)

Singh, R.N.; Stahle, P.; Sairam, K.; Ristmana, Matti; Banerjee, S.

2008-01-01

The objective of the present investigation is to predict the habit plane of δ-hydride precipitating in α-Zr at 25 and 300 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 of zirconium and its hydride 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 using materials properties reported at 25 and 300 deg C. Contrary to several habit planes reported in literature for δ-hydrides precipitating in α-Zr crystal the total accommodation energy minima suggests only basal plane i.e. (0001) as the habit plane. (author)

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)

Preliminary data from lithium hydride ablation tests conducted by NASA, Ames Research Center

International Nuclear Information System (INIS)

Elliott, R.D.

1970-01-01

A series of ablation tests of lithium hydride has been made by NASA-Ames in one of their high-enthalpy arc-heated wind tunnels. Two-inch diameter cylindrical samples of the hydride, supplied by A. I., were subjected to heating on their ends for time periods up to 10 seconds. After each test, the amount of material removed from each sample was measured. The rates of loss of material were correlated with the heat input rates in terms of a heat of ablation, which ranged from 2100 to 3500 Btu/lb. The higher values were obtained when the hydride contained a matrix such as steel honeycomb of steel wool. (U.S.)

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.)

A novel magnesium-vanadium hydride synthesized by a gigapascal-high-pressure technique

Energy Technology Data Exchange (ETDEWEB)

Kyoi, Daisuke; Sato, Toyoto; Roennebro, Ewa; Tsuji, Yasufumi; Kitamura, Naoyuki; Ueda, Atsushi; Ito, Mikio; Katsuyama, Shigeru; Hara, Shigeta; Noreus, Dag; Sakai, Tetsuo

2004-07-28

A magnesium-based vanadium-doped hydride was prepared in a high-pressure anvil cell by reacting a MgH{sub 2}-25%V molar mixture at 8 GPa and 873 K. The new magnesium-vanadium hydride has a cubic F-centred substructure (a=4.721(1) Angst), with an additional superstructure, which could be described by a doubling of the cubic cell axis and a magnesium atom framework, including an ordered arrangement of both vanadium atoms and vacancies (a=9.437(3) Angst, space group Fm3-bar m (no. 225), Z=4, V=840.55 Angst{sup 3}). The metal atom structure is related to the Ca{sub 7}Ge type structure but the refined metal atom composition with vacancies on one of the magnesium sites corresponding to Mg{sub 6}V nearly in line with EDX analysis. The thermal properties of the new compound were also studied by TPD analysis and TG-DTA. The onset of the hydrogen desorption for the new Mg{sub 6}V hydride occurred at a 160 K lower temperature when compared to magnesium hydride at a heating rate of 10 K/min.

Catalitic effect of Co on hydrogen desorption form nanostucturated magnesium hydride

Directory of Open Access Journals (Sweden)

Matović Ljiljana Lj.

2008-01-01

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

A new oxidimetric reagent: potassium dichromate in a strong phosphoric acid medium--VII. Photometric titration of vanadium(IV) and of cerium(III) alone and in mixtures with iroN(II).

Science.gov (United States)

Rao, G G; Rao, P K

1967-01-01

Vanadium(IV) can be accurately titrated with potassium dichromate in media containing phosphoric acid of 3-12M concentration: the change in absorption of vanadium(IV) is followed in the region 660 mmicro using a red filter. It is more convenient to carry out the titration in 3M phosphoric acid because at higher concentrations chloride, nitrate, cerium(III) and manganese(II) may interfere. Photoelcetric titration is more convenient than potentiometric because the former can be made in a 3M phosphoric acid medium, whereas the latter is possible only in 12M phosphoric acid. The simultaneous differential photometric titration of iron(II) and vanadium(IV) is also possible. Conditions have been found for the photometric titration of cerium(III) and of cerium(III) plus iron(II). The titration is carried out (at 450 mmicro or with a blue filter) in about 10.5M phosphoric acid. Application of the method to a cerium mineral is considered.

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

Energy Technology Data Exchange (ETDEWEB)

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

1998-08-01

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

Room temperature and thermal decomposition of magnesium hydride/deuteride thin films

Energy Technology Data Exchange (ETDEWEB)

Ares, J.R.; Leardini, F.; Bodega, J.; Macia, M.D.; Diaz-Chao, P.; Ferrer, I.J.; Fernandez, J.F.; Sanchez, C. [Universidad Autonoma de Madrid (Spain). Lab. de Materiales de Interes en Energias Renovables

2010-07-01

Magnesium hydride (MgH{sub 2}) can be considered an interesting material to store hydrogen as long as two main drawbacks were solved: (i) its high stability and (ii) slow (de)hydriding kinetics. In that context, magnesium hydride films are an excellent model system to investigate the influence of structure, morphology and dimensionality on kinetic and thermodynamic properties. In the present work, we show that desorption mechanism of Pd-capped MgH{sub 2} at room temperature is controlled by a bidimensional interphase mechanism and a similar rate step limiting mechanism is observed during thermal decomposition of MgH{sub 2}. This mechanism is different to that occurring in bulk MgH{sub 2} (nucleation and growth) and obtained activation energies are lower than those reported in bulk MgH{sub 2}. We also investigated the Pd-capping properties upon H-absorption/desorption by means of RBS and isotope experiments. (orig.)

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

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.

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

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)

U-8 wt %Mo and 7 wt %Mo alloys powder obtained by an hydride-de hydride process; Obtencion de polvo de aleaciones U-8% Mo y U-7% Mo (en peso) mediante hidruracion

Energy Technology Data Exchange (ETDEWEB)

Balart, Silvia N; Bruzzoni, Pablo; Granovsky, Marta S; Gribaudo, Luis M.J.; Hermida, Jorge D; Ovejero, Jose; Rubiolo, Gerardo H; Vicente, Eduardo E [Comision Nacional de Energia Atomica, General San Martin (Argentina). Dept. de Materiales

2000-07-01

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-{alpha} phase to transform to UH{sub 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 {gamma} -phase to {alpha} -phase. Subsequent hydriding transforms this {alpha} -phase to UH{sub 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)

Effects of H-H interactions on the heat of H absorption by β and delta Zr hydrides

International Nuclear Information System (INIS)

Ohta, Yutaka; Mabuchi, Mahito; Naito, Shizuo; Hashino, Tomoyasu

1987-01-01

The heat of H absorption by β and delta Zr hydrides has been measured by isoperibol calorimetry over the range of H concentration 0.1 - 1.6 H/Zr at temperatures 873-1273 K. In the β hydride the heat per H atom (differential heat) increases and then decreases as the H concentration increases. In the delta hydride only a decrease at large H concentrations is clearly observed. The increase in the β hydride is related by self-consistent calculations to a pair indirect interaction between H atoms; the decreases in the β and delta hydrides are due to a pair direct interaction which is of the form of a screened Coulomb potential. The differential heat is estimated from the pair indirect and direct interactions by the use of Monte Carlo simulations and compared with the measured differential heat. (author)

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.)

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.

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)

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

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

Probabilistic modeling of material resistance to crack initiation due to hydrided region overloads in CANDU Zr-2.5%Nb pressure tubes

International Nuclear Information System (INIS)

Gutkin, L.; Scarth, D.A.

2014-01-01

Zr-2.5%Nb pressure tubes in CANDU nuclear reactors are susceptible to hydride-assisted cracking at the locations of stress concentration, such as in-service flaws. Probabilistic methodology is being developed to evaluate such flaws for crack initiation due to hydrided region overloads, which occur when the applied stress acting on a flaw with an existing hydrided region at its tip exceeds the stress at which the hydrided region is formed. As part of this development, probabilistic modeling of pressure tube material resistance to overload crack initiation has been performed on the basis of a set of test data specifically designed to study the effects of non-ratcheting hydride formation conditions and load reduction prior to hydride formation. In the modeling framework, the overload resistance is represented as a power-law function of the material resistance to initiation of delayed hydride cracking under constant loading, where both the overload crack initiation coefficient and the overload crack initiation exponent vary with the flaw geometry. In addition, the overload crack initiation coefficient varies with the extent of load reduction prior to hydride formation as well as the number of non-ratcheting hydride formation thermal cycles. (author)

Probabilistic modeling of material resistance to crack initiation due to hydrided region overloads in CANDU Zr-2.5%Nb pressure tubes

Energy Technology Data Exchange (ETDEWEB)

Gutkin, L.; Scarth, D.A. [Kinectrics Inc., Toronto, ON (Canada)

2014-07-01

Zr-2.5%Nb pressure tubes in CANDU nuclear reactors are susceptible to hydride-assisted cracking at the locations of stress concentration, such as in-service flaws. Probabilistic methodology is being developed to evaluate such flaws for crack initiation due to hydrided region overloads, which occur when the applied stress acting on a flaw with an existing hydrided region at its tip exceeds the stress at which the hydrided region is formed. As part of this development, probabilistic modeling of pressure tube material resistance to overload crack initiation has been performed on the basis of a set of test data specifically designed to study the effects of non-ratcheting hydride formation conditions and load reduction prior to hydride formation. In the modeling framework, the overload resistance is represented as a power-law function of the material resistance to initiation of delayed hydride cracking under constant loading, where both the overload crack initiation coefficient and the overload crack initiation exponent vary with the flaw geometry. In addition, the overload crack initiation coefficient varies with the extent of load reduction prior to hydride formation as well as the number of non-ratcheting hydride formation thermal cycles. (author)

Synthesis and characterization of an iron complex bearing a cyclic tetra-N-heterocyclic carbene ligand: An artifical heme analogue?

KAUST Repository

Anneser, Markus R.

2015-04-20

An iron(II) complex with a cyclic tetradentate ligand containing four N-heterocyclic carbenes was synthesized and characterized by means of NMR and IR spectroscopies, as well as by single-crystal X-ray structure analysis. The iron center exhibits an octahedral coordination geometry with two acetonitrile ligands in axial positions, showing structural analogies with porphyrine-ligated iron complexes. The acetonitrile ligands can readily be substituted by other ligands, for instance, dimethyl sulfoxide, carbon monoxide, and nitric oxide. Cyclic voltammetry was used to examine the electronic properties of the synthesized compounds. © 2015 American Chemical Society.

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.

Zirconium-hydride solid zero power reactor and its application research

International Nuclear Information System (INIS)

Lin Shenghuo; Luo Zhanglin; Su Zhuting

1994-10-01

The Zirconium Hydride Solid Zero Power Reactor built at China Institute of Atomic Energy is introduced. In the reactor Zirconium-hydride is used as moderator, plexiglass as reflector and U 3 O 8 with enrichment of 20% as the fuel, Since its initial criticality, the physical characteristics and safety features have been measured with the result showing that the reactor has sound stability and high sensitivity, etc. It has been successfully used for the personnel training and for the testing of reactor control instruments and experiment devices. It also presents the special advantage for the pre-research of some applications

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)

Effect of hydrides on the ductile-brittle transition in stress-relieved, recrystallized and beta-treated zircaloy-4

International Nuclear Information System (INIS)

Pelchat, J.; Barcelo, F.

1991-01-01

This paper is concerned with the influence of δ-hydrides on the mechanical properties of three heat treated cold-rolled Zircaloy-4 sheets (stress-relieved, recrystallized and β treated), tested at room temperature and 350 0 C. Smooth tensile specimens of two thicknesses: 0.5 and 3.1 mm, containing different hydride volume fractions, up to 18% (about 1400 ppm H), have been tested. Metallographic and fractographic analysis were carried out in order to examine the fracture morphology near and on the fracture surface, and to determine the evolution of the fracture mechanism of hydrides as a function of temperature, hydride orientation and volume fraction

In-situ study of hydriding kinetics in Pd-based thin film systems

Energy Technology Data Exchange (ETDEWEB)

Delmelle, Renaud; Proost, Joris [Univ. Catholique de Louvain, Louvain-la-Neuve (Belgium). Div. of Materials and Process Engineering

2010-07-01

The hydriding kinetics of Pd thin films has been investigated in detail. The key experimental technique used in this work consists of a high resolution curvature measurement setup, which continuously monitors the reflections of multiple laser beams coming off a cantilevered sample. After mounting the sample inside a vacuum chamber, a H-containing gas mixture is introduced to instantaneously generate a given hydrogen partial pressure (p{sub H2}) inside the chamber. The resulting interaction of H with the Pd layer then leads to a volume expansion of the thin film system. This induces in turn changes in the sample curvature as a result of internal stresses developing in the Pd film during a hydriding cycle. Based on such curvature date obtained in-situ at different p{sub H2}, a two-step model for the kinetics of Pd-hydride formation has been proposed and expressions for the hydrogen adsorption and absorption velocities have been derived. The rate-limiting steps have been identified by studying the p{sub H2}-dependence of these velocities. Furthermore, from our in-situ experimental data, relevant kinetic parameters have been calculated. The effect of dry air exposure of the Pd films on the hydriding kinetics has been considered as well. (orig.)

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)

Interaction of electrons with light metal hydrides in the transmission electron microscope.

Science.gov (United States)

Wang, Yongming; Wakasugi, Takenobu; Isobe, Shigehito; Hashimoto, Naoyuki; Ohnuki, Somei

2014-12-01

Transmission electron microscope (TEM) observation of light metal hydrides is complicated by the instability of these materials under electron irradiation. In this study, the electron kinetic energy dependences of the interactions of incident electrons with lithium, sodium and magnesium hydrides, as well as the constituting element effect on the interactions, were theoretically discussed, and electron irradiation damage to these hydrides was examined using in situ TEM. The results indicate that high incident electron kinetic energy helps alleviate the irradiation damage resulting from inelastic or elastic scattering of the incident electrons in the TEM. Therefore, observations and characterizations of these materials would benefit from increased, instead decreased, TEM operating voltage. © The Author 2014. Published by Oxford University Press on behalf of The Japanese Society of Microscopy. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

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

OpenAIRE

Xu, Shanna; Dong, Junhua; Ke, Wei

2010-01-01

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

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

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

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

Determination of plutonium by secondary coulometric titration with internally generated iron(II) Pt. 2

International Nuclear Information System (INIS)

Chitnis, R.T.; Talnikar, S.G.; Thakur, V.A.; Paranjape, A.H.

1979-01-01

Determination of plutonium by secondary coulometry involving the controlled potential technique for the generation of an iron(II) mediator, is reported in Part I. In this paper, the same determination is reported using constant current coulometry for the generation of the mediator, and zero current potentiometry for end-point detection. The factors affecting the current efficiency, viz. current density and supporting electrolyte composition have been checked in order to define the appropriate conditions for obtaining 100% current efficiency. The original method of Carson et al. suffers from the disadvantage that it involves complicated sample treatment. Introduction of perchloric acid treatment as a method for the oxidation of plutonium and the pretitration of the supporting electrolyte to the end-point potential prior to sample addition, have considerably helped to improve the precision and accuracy of the method. Exhaustive analytical data are reported covering plutonium quantities ranging from 25 micrograms to 5 milligrams, which establishes the scope of the method. (author)

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

Energy Technology Data Exchange (ETDEWEB)

Martin Rengel, M.A., E-mail: mamartin.rengel@upm.es [E.T.S.I. Caminos, Canales y Puertos, Universidad Politécnica de Madrid, c/ Profesor Aranguren, 3, E-28040 Madrid (Spain); Gomez, F.J., E-mail: javier.gomez@amsimulation.com [Advanced Material Simulation, AMS, Bilbao (Spain); Rico, A., E-mail: alvaro.rico@urjc.es [DIMME, Universidad Rey Juan Carlos, Mostoles (Spain); Ruiz-Hervias, J. [E.T.S.I. Caminos, Canales y Puertos, Universidad Politécnica de Madrid, c/ Profesor Aranguren, 3, E-28040 Madrid (Spain); Rodriguez, J. [DIMME, Universidad Rey Juan Carlos, Mostoles (Spain)

2017-04-15

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

Hydriding and structural characteristics of thermally cycled and cold-worked V-0.5 at.%C alloy

International Nuclear Information System (INIS)

Chandra, Dhanesh; Sharma, Archana; Chellappa, Raja; Cathey, William N.; Lynch, Franklin E.; Bowman, Robert C.; Wermer, Joseph R.; Paglieri, Stephen N.

2008-01-01

High pressure hydrides of V 0.995 C 0.005 were thermally cycled between β 2 - and γ-phases hydrides for potential use in cryocoolers/heat pumps for space applications. The effect of addition of carbon to vanadium, on the plateau enthalpies of the high pressure β 2 + γ region is minimal. This is in contrast to the calculated plateau enthalpies for low pressure (α + β 1 ) mixed phases which showed a noticeable lowering of the values. Thermal cycling between β 2 -and γ-phase hydrides increased the absorption pressures but desorption pressure did not change significantly and the free energy loss due to hysteresis also increased. Hydriding of the alloy with prior cold-work increased the pressure hysteresis significantly and lowered the hydrogen capacity. In contrast to the alloy without any prior straining (as-cast), desorption pressure of the alloy with prior cold-work also decreased significantly. Microstrains, 2 > 1/2 , in the β 2 -phase lattice of the thermally cycled hydrides decreased after 778 cycles and the domain sizes increased. However, in the γ-phase, both the microstrains and the domain sizes decreased after thermal cycling indicating no particle size effect. The dehydrogenated α-phase after 778 thermal cycles also showed residual microstrains in the lattice, similar to those observed in intermetallic hydrides. The effect of thermal cycling (up to 4000 cycles between β 2 - and γ-phases) and cold working on absorption/desorption pressures, hydrogen storage capacity, microstrains, long-range strains, and domain sizes of β 2 - and γ-phase hydrides of V 0.995 C 0.005 alloys are presented

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

International Nuclear Information System (INIS)

Clayton, J.C.

1987-10-01

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

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

Directory of Open Access Journals (Sweden)

Shanna Xu

2010-01-01

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

Azimuthally anisotropic hydride lens structures in Zircaloy 4 nuclear fuel cladding: High-resolution neutron radiography imaging and BISON finite element analysis

Science.gov (United States)

Lin, Jun-Li; Zhong, Weicheng; Bilheux, Hassina Z.; Heuser, Brent J.

2017-12-01

High-resolution neutron radiography has been used to image bulk circumferential hydride lens particles in unirradiated Zircaloy 4 tubing cross section specimens. Zircaloy 4 is a common light water nuclear reactor (LWR) fuel cladding; hydrogen pickup, hydride formation, and the concomitant effect on the mechanical response are important for LWR applications. Ring cross section specimens with three hydrogen concentrations (460, 950, and 2830 parts per million by weight) and an as-received reference specimen were imaged. Azimuthally anisotropic hydride lens particles were observed at 950 and 2830 wppm. The BISON finite element analysis nuclear fuel performance code was used to model the system elastic response induced by hydride volumetric dilatation. The compressive hoop stress within the lens structure becomes azimuthally anisotropic at high hydrogen concentrations or high hydride phase fraction. This compressive stress anisotropy matches the observed lens anisotropy, implicating the effect of stress on hydride formation as the cause of the observed lens azimuthal asymmetry. The cause and effect relation between compressive stress and hydride lens anisotropy represents an indirect validation of a key BISON output, the evolved hoop stress associated with hydride formation.

The influence of stress state on the reorientation of hydrides in a zirconium alloy

International Nuclear Information System (INIS)

Cinbiz, Mahmut N.; Koss, Donald A.; Motta, Arthur T.

2016-01-01

Hydride reorientation can occur in spent nuclear fuel cladding when subjected to a tensile hoop stress above a threshold value during cooling. Because in these circumstances the cladding is under a multiaxial stress state, the effect of stress biaxiality on the threshold stress for hydride reorientation is investigated using hydrided CWSR Zircaloy-4 sheet specimens containing ∼180 wt ppm of hydrogen and subjected to a two-cycle thermo-mechanical treatment. The study is based on especially designed specimens within which the stress biaxiality ratios range from uniaxial (σ_2/σ_1 = 0) to “near-equibiaxial” tension (σ_2/σ_1 = 0.8). The threshold stress is determined by mapping finite element calculations of the principal stresses and of the stress biaxiality ratio onto the hydride microstructure obtained after the thermo-mechanical treatment. The results show that the threshold stress (maximum principal stress) decreases from 155 to 75 MPa as the stress biaxiality increases from uniaxial to “near-equibiaxial” tension.

ORGANOMETALLIC IRON(II) COMPLEXES CONTAINING P-SUBSTITUTED ACETOPHENONE-ARYLHYDRAZONE LIGANDS

OpenAIRE

Manzur, Carolina; Millán, Lorena; Figueroa, Walter; Hamon, Jean-René; Mata, Jose A.; Carrillo, David

2002-01-01

A series of twelve new organometallic acetophenone-hydrazone complexes of general formula [(h 5-Cp)Fe(h 6-o-RC6H4)-NHN=CMe-C6H4-p-R’]+PF6- (Cp= C5H5; R,R’=H,Me, [5]+PF6-; H,MeO, [6]+PF6-; H,NMe2, [7]+PF6-; Me,Me, [8]+PF6-; Me,MeO, [9]+PF6-; Me,NMe2, [10]+PF6-; MeO,Me, [11]+PF6-; MeO,MeO, [12]+PF6-; MeO,NMe2, [13]+PF6-; Cl,Me, [14]+PF6-; Cl,MeO, [15]+PF6-; Cl,NMe2, [16]+PF6-) has been prepared by reaction between their corresponding organometallic hydrazine precursors [(h 5-Cp)Fe(h 6-o-RC6H4)-...

A new ternary magnesium-titanium hydride Mg{sub 7}TiH{sub x} with hydrogen desorption properties better than both binary magnesium and titanium hydrides

Energy Technology Data Exchange (ETDEWEB)

Kyoi, Daisuke; Sato, Toyoto; Roennebro, Ewa; Kitamura, Naoyuki; Ueda, Atsushi; Ito, Mikio; Katsuyama, Shigeru; Hara, Shigeta; Noreus, Dag; Sakai, Tetsuo

2004-06-09

A magnesium based titanium doped hydride was prepared in a high-pressure anvil cell by reacting a mixture of MgH{sub 2} and TiH{sub 1.9} at 8 GPa and 873 K. The metal structure has a Ca{sub 7}Ge type structure (a=9.532(2) A, space group Fm3-barm (no. 225), Z=4, V=866.06 A{sup 3}). The refined metal atom composition Mg{sub 7}Ti was almost in line with EDS analysis. This means that the new magnesium-titanium hydride has a structure that is more related to TiH{sub 1.9} than to MgH{sub 2}. The thermal properties of the new compound were also studied by TPD analysis. The new hydride, Mg{sub 7}TiH{sub x} exhibits 5.5 mass% (x{approx}12.7) and decomposes into Mg and TiH{sub 1.9} upon releasing 4.7 mass% of hydrogen around 605 K, that is at a 130 and 220 K lower desorption temperature compared to MgH{sub 2} and TiH{sub 1.9}, respectively.

Manufacturing and investigation of U-Mo LEU fuel granules by hydride-dehydride processing

International Nuclear Information System (INIS)

Stetskiy, Y.A.; Trifonov, Y.I.; Mitrofanov, A.V.; Samarin, V.I.

2002-01-01

Investigations of hydride-dehydride processing for comminution of U-Mo alloys with Mo content in the range 1.9/9.2% have been performed. Some regularities of the process as a function of Mo content have been determined as well as some parameters elaborated. Hydride-dehydride processing has been shown to provide necessary phase and chemical compositions of U-Mo fuel granules to be used in disperse fuel elements for research reactors. Pin type disperse mini-fuel elements for irradiation tests in the loop of 'MIR' reactor (Dmitrovgrad) have been fabricated using U-Mo LEU fuel granules obtained by hydride-dehydride processing. Irradiation tests of these mini-fuel elements loaded to 4 g U tot /cm 3 are planned to start by the end of this year. (author)

Poisoning Experiments Aimed at Discriminating Active and Less-Active Sites of Silica-Supported Tantalum Hydride for Alkane Metathesis

KAUST Repository

Saggio, Guillaume

2010-10-04

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 in the global turnover. Conversely, cyclopentane induces no such selective poisoning. Hence, the active tantalum hydride sites that show greater resistance to oxygen poisoning correspond to the νTa-H bands of higher wavenumbers, particularly that at 1860cm-1. These active tantalum hydride sites should correspond to tris- or monohydride species relatively far from silica surface oxygen atoms. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Ab initio lattice dynamics of complex structures

DEFF Research Database (Denmark)

Voss, Johannes

2008-01-01

In this thesis, density functional theory is applied in a study of thermodynamic properties of so-called complex metal hydrides, which are promising materials for hydrogen storage applications. Since the unit cells of these crystals can be relatively large with many symmetrically inequivalent ato...

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

Determination of the population of octahedral and tetrahedral interstitials in zirconium hydrides

International Nuclear Information System (INIS)

Fedorov, V.M.; Gogava, V.V.; Shilo, S.I.; Biryukova, E.A.

1983-01-01

Results of neutron investigations of ZrHsub(1.66), ZrHsub(1.75) and ZrHsub(1.98) zirconium hydrides are presented. Investigations were conducted using plane polycrystal samples by multidetector system of scattered neutron detection. Neutron diffraction method was used to determine the number of interstitial hydrogen atoms in interstitials of the lattice cell in the case of statistic atom distribution. The numbers of interstitial atoms in octahedral interstitials for zirconium hydrides were determined experimentally; the difference of potential energies of hydrogen atoms in octa- and tetrahedral interstitials was determined as well. It is shown that experimentally determined difference of potential energies of hydrogen atoms, occupying octa- and tetrahedral positions in investigated zirconium hydrides results at room temperature in the pretailing occupation of tetrahedral interstitials by hydrogen atoms (85-90%); the occupation number grows with temperature decrease and the ordering of interstitial vacancies with formation of hydrogen superstructure takes place at low temperatures

Hydriding and dehydriding characteristics of small-scale DU and ZrCo beds

Energy Technology Data Exchange (ETDEWEB)

Chung, Dongyou; Lee, Jungmin; Koo, Daeseo [Korea Atomic Energy Research Institute, 989-111 Daedeokdaero, Yuseong, Daejeon 305-353 (Korea, Republic of); Chung, Hongsuk, E-mail: hschung1@kaeri.kr [Korea Atomic Energy Research Institute, 989-111 Daedeokdaero, Yuseong, Daejeon 305-353 (Korea, Republic of); Kim, Ki Hwan [Korea Atomic Energy Research Institute, 989-111 Daedeokdaero, Yuseong, Daejeon 305-353 (Korea, Republic of); Kang, Hyun-Goo; Chang, Min Ho [National Fusion Research Institute, 113 Gwahakro, Yuseong, Daejeon 305-333 (Korea, Republic of); Camp, Patrick [ITER Organization, Route de Vinon sur Verdon, 13115 Saint Paul Lez Durance (France); Jung, Ki Jung; Cho, Seungyon; Yun, Sei-Hun; Kim, Chang Shuk [National Fusion Research Institute, 113 Gwahakro, Yuseong, Daejeon 305-333 (Korea, Republic of); Yoshida, Hiroshi [Fusion Science Consultant, 3288-10 Sakado-cho, Mito-shi 310-0841, Ibakaki-ken (Japan); Paek, Seungwoo; Lee, Hansoo [Korea Atomic Energy Research Institute, 989-111 Daedeokdaero, Yuseong, Daejeon 305-353 (Korea, Republic of)

2013-10-15

Highlights: • We have designed and fabricated a twosome small-scale getter bed for a comparison of ZrCo with DU on the hydriding/dehydriding properties. • We provide preliminary experimental results of our ZrCo and DU beds. -- Abstract: With the development of fusion technology, it will be necessary to store large amounts of tritium during the nuclear fusion fuel cycle. Stable metal tritides are viewed as potential candidates for the high-density storage of tritium. Metal tritide formers offer a safe and convenient method for tritium storage. For the storage, supply, and recovery of hydrogen isotopes, zirconium cobalt (ZrCo) and depleted uranium (DU) have been extensively proposed. Thus, we have designed and fabricated two identical small-scale getter beds for a comparison of ZrCo with DU on the hydriding/dehydriding properties. After the powderization of the metals, the hydriding/dehydriding performance at different stoichiometries of ZrCo and DU was measured. We provide preliminary experimental results of our ZrCo and DU beds.

A Synthetic Single-Site Fe Nitrogenase: High Turnover, Freeze-Quench (57)Fe Mössbauer Data, and a Hydride Resting State.

Science.gov (United States)

Del Castillo, Trevor J; Thompson, Niklas B; Peters, Jonas C

2016-04-27

The mechanisms of the few known molecular nitrogen-fixing systems, including nitrogenase enzymes, are of much interest but are not fully understood. We recently reported that Fe-N2 complexes of tetradentate P3(E) ligands (E = B, C) generate catalytic yields of NH3 under an atmosphere of N2 with acid and reductant at low temperatures. Here we show that these Fe catalysts are unexpectedly robust and retain activity after multiple reloadings. Nearly an order of magnitude improvement in yield of NH3 for each Fe catalyst has been realized (up to 64 equiv of NH3 produced per Fe for P3(B) and up to 47 equiv for P3(C)) by increasing acid/reductant loading with highly purified acid. Cyclic voltammetry shows the apparent onset of catalysis at the P3(B)Fe-N2/P3(B)Fe-N2(-) couple and controlled-potential electrolysis of P3(B)Fe(+) at -45 °C demonstrates that electrolytic N2 reduction to NH3 is feasible. Kinetic studies reveal first-order rate dependence on Fe catalyst concentration (P3(B)), consistent with a single-site catalyst model. An isostructural system (P3(Si)) is shown to be appreciably more selective for hydrogen evolution. In situ freeze-quench Mössbauer spectroscopy during turnover reveals an iron-borohydrido-hydride complex as a likely resting state of the P3(B)Fe catalyst system. We postulate that hydrogen-evolving reaction activity may prevent iron hydride formation from poisoning the P3(B)Fe system. This idea may be important to consider in the design of synthetic nitrogenases and may also have broader significance given that intermediate metal hydrides and hydrogen evolution may play a key role in biological nitrogen fixation.

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...

Application of hafnium hydride control rod to large sodium cooled fast breeder reactor

Energy Technology Data Exchange (ETDEWEB)

Ikeda, Kazumi, E-mail: kazumi_ikeda@mfbr.mhi.co.jp [Mitsubishi FBR Systems, Inc., 34-17, Jingumae 2-Chome, Shibuya-ku, Tokyo 150-0001 (Japan); Moriwaki, Hiroyuki, E-mail: hiroyuki_moriwaki@mfbr.mhi.co.jp [Mitsubishi FBR Systems, Inc., 34-17, Jingumae 2-Chome, Shibuya-ku, Tokyo 150-0001 (Japan); Ohkubo, Yoshiyuki, E-mail: yoshiyuki_okubo@mfbr.mhi.co.jp [Mitsubishi FBR Systems, Inc., 34-17, Jingumae 2-Chome, Shibuya-ku, Tokyo 150-0001 (Japan); Iwasaki, Tomohiko, E-mail: tomohiko.iwasaki@qse.tohoku.ac.jp [Department of Quantum Science and Energy Engineering, Tohoku University, Aoba, Aramaki, Aoba-ku, Sendai-shi, Miyagi-ken 980-8579 (Japan); Konashi, Kenji, E-mail: konashi@imr.tohoku.ac.jp [Institute for Materials Research, Tohoku University, Narita-cho, Oarai-machi, Higashi-Ibaraki-gun, Ibaraki-ken 311-1313 (Japan)

2014-10-15

Highlights: • Application of hafnium hydride control rod to large sodium cooled fast breeder reactor. • This paper treats application of an innovative hafnium hydride control rod to a large sodium cooled fast breeder reactor. • Hydrogen absorption triples the reactivity worth by neutron spectrum shift at H/Hf ratio of 1.3. • Lifetime of the control rod quadruples because produced daughters of hafnium isotopes are absorbers. • Nuclear and thermal hydraulic characteristics of the reactor are as good as or better than B-10 enriched boron carbide. - Abstract: This study treats the feasibility of long-lived hafnium hydride control rod in a large sodium-cooled fast breeder reactor by nuclear and thermal analyses. According to the nuclear calculations, it is found that hydrogen absorption of hafnium triples the reactivity by the neutron spectrum shift at the H/Hf ratio of 1.3, and a hafnium transmutation mechanism that produced daughters are absorbers quadruples the lifetime due to a low incineration rate of absorbing nuclides under irradiation. That is to say, the control rod can function well for a long time because an irradiation of 2400 EFPD reduces the reactivity by only 4%. The calculation also reveals that the hafnium hydride control rod can apply to the reactor in that nuclear and thermal characteristics become as good as or better than 80% B-10 enriched boron carbide. For example, the maximum linear heat rate becomes 3% lower. Owing to the better power distribution, the required flow rate decreases approximately by 1%. Consequently, it is concluded on desk analyses that the long lived hafnium hydride control rod is feasible in the large sodium-cooled fast breeder reactor.

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)

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

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

Synthesis, crystal structure and reactivity studies of iron complexes with pybox ligands

KAUST Repository

Chen, Tao; Yang, Limin; Gong, Dirong; Huang, Kuo-Wei

2014-01-01

Iron(II) complexes, [Fe(2,6-bis(4,4-dimethyl-1,3-oxazolin-2-yl)pyridine)Cl2] ((Fe(Me2-pybox)Cl2), 3) and [Fe(2,6-bis(4,4-diphenyl-1,3-oxazolin-2-yl)pyridine)Cl2] ((Fe(Ph2-pybox)Cl2), 4), have been synthesized and characterized by X-ray crystallographic analysis. Upon treatment of complex 3 with silver triflate and 4 with acetonitrile, [Fe(Me2-pybox)(CH3CN)OTf2] (5) and [Fe(Ph2-pybox)(CH3CN)2Cl][FeCl3] (6) were obtained, respectively. The bulkier phenyl substitutes were found not only to cause the elongation of the N-Fe bonds but also influence the reactivity of the Fe center.

Synthesis, crystal structure and reactivity studies of iron complexes with pybox ligands

KAUST Repository

Chen, Tao

2014-11-01

Iron(II) complexes, [Fe(2,6-bis(4,4-dimethyl-1,3-oxazolin-2-yl)pyridine)Cl2] ((Fe(Me2-pybox)Cl2), 3) and [Fe(2,6-bis(4,4-diphenyl-1,3-oxazolin-2-yl)pyridine)Cl2] ((Fe(Ph2-pybox)Cl2), 4), have been synthesized and characterized by X-ray crystallographic analysis. Upon treatment of complex 3 with silver triflate and 4 with acetonitrile, [Fe(Me2-pybox)(CH3CN)OTf2] (5) and [Fe(Ph2-pybox)(CH3CN)2Cl][FeCl3] (6) were obtained, respectively. The bulkier phenyl substitutes were found not only to cause the elongation of the N-Fe bonds but also influence the reactivity of the Fe center.

Hydrides blister formation and induced embrittlement on zircaloy-4 cladding tubes in reactivity initiated conditions

International Nuclear Information System (INIS)

Hellouin-De-Menibus, A.

2012-01-01

Our aim is to study the cladding fracture with mechanical tests more representative of RIA conditions, taking into account the hydrides blisters, representative strain rates and stress states. To obtain hydride blisters, we developed a thermodiffusion setup that reproduces blister growth in reactor conditions. By metallography, nano-hardness, XRD and ERDA, we showed that they are constituted by 80% to 100% of δ hydrides in a Zircaloy-4 matrix, and that the zirconium beneath has some radially oriented hydrides. We modeled the blister growth kinetics taking into account the hysteresis of the hydrogen solubility limit and defined the thermal gradient threshold for blister growth. The modeling of the dilatometric behavior of hydrided zirconium indicates the important role of the material crystallographic texture, which could explain differences in the blister shape. Mechanical tests monitored with an infrared camera showed that significant local heating occurred at strain rates higher than 0.1/s. In parallel, the Expansion Due to Compression test was optimized to increase the bi-axiality level from uniaxial stress to plane strain (HB-EDC and VHB-EDC tests). This increase in loading bi-axiality lowers greatly the fracture strain at 25 C and 350 C only in homogeneous material without blister. Eventually, the ductility decrease of unirradiated Zircaloy-4 cladding tube in function of the blister depth was quantified. (author) [fr

Iron(II)-catalyzed intramolecular aminohydroxylation of olefins with functionalized hydroxylamines.

Science.gov (United States)

Liu, Guan-Sai; Zhang, Yong-Qiang; Yuan, Yong-An; Xu, Hao

2013-03-06

A diastereoselective aminohydroxylation of olefins with a functionalized hydroxylamine is catalyzed by new iron(II) complexes. This efficient intramolecular process readily affords synthetically useful amino alcohols with excellent selectivity (dr up to > 20:1). Asymmetric catalysis with chiral iron(II) complexes and preliminary mechanistic studies reveal an iron nitrenoid is a possible intermediate that can undergo either aminohydroxylation or aziridination, and the selectivity can be controlled by careful selection of counteranion/ligand combinations.

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...

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.

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.)

A study of fundamental reaction pathways for transition metal alkyl complexes. I. The reaction of a nickel methyl complex with alkynes. Ii. The mechanism of aldehyde formation in the reaction of a molybdenum hydride with molybdenum alkyls

Energy Technology Data Exchange (ETDEWEB)

Huggins, John Mitchell [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)

1980-06-12

it was possible to show that the mixed dimers MeCpMo(CO)₃-(CO)₃MoCp (3b) and MeCpMo(CO)₂≡(CO)₂ MoCp (4b) are the predominant kinetic products of the reaction. Additionally labeling the carbonyl ligands of 1a with ¹³CO led to the conclusion that all three of the carbonyl ligands in 1a end up in the tetracarbonyl dimers 4a if the reaction is carried out under a continuous purge of argon Trapping studies failed to find any evidence for the intermediacy of either [CpMo(CO)₃] ^- or [CpMo(CO)₃] ⁺ in this reaction. A mechanism is proposed that involves the initial migration of the alkyl ligand in 2 to CO forming an unsaturated acyl complex which reacts with 1a to give a binuclear complex containing a three center-two electron Mo-H-Mo bond. This complex then selectively looses a carbonyl from the acyl molybdenum, migrates the hydride to that same metal, and forms a metal-metal bond. This binuclear complex with the hydride and acyl ligands on one metal reductively eliminates aldehyde, and migrates a carbonyl ligand, to give 4a directly. The other product 3a is formed by addition of two molecules of free CO to 4a.

Transmission Electron Microscopy Studies on Titanium-doped Sodium Aluminum Hydride

Science.gov (United States)

Culnane, Lance F.

Hydrogen fuel cells play an important role in today's diverse and blossoming alternative energy industry. One of the greatest technological barriers for vehicular applications is the storage of hydrogen (which is required to power hydrogen fuel cells). Storing hydrogen as a gas is not volume efficient, and storing it as a liquid is not cost effective, therefore solid-state storage of hydrogen, such as in metal hydrides offers the most potential for success since many metal hydrides have attractive qualities for hydrogen storage such as: high volumetric capacity, cost efficiency, weight efficiency, low refueling times, and most importantly, high safety. Unfortunately, a compound has not been discovered which contains all of the attractive hydrogen storage qualities for vehicular applications. Sodium aluminum hydride (NaAlH 4) is one of the few compounds which is close to meeting requirements for car manufacturers, and has perhaps been researched the most extensively out of all metal hydrides in the last 15 years. This arises from the remarkable discovery by Bogdanovic who found that doping NaAlH4 with Ti dopants enabled the reversible dehydrogenation and hydrogenation of NaAlH 4 at mild conditions. Various evidence and theories have been proposed to suggest explanations for the enhanced kinetic effect that Ti-doping and ball-milling provide. However, the research community has not reached a consensus as to the exact role of Ti-dopants. If the role of titanium in the NaAlH4 dehydrogenation/hydrogenation mechanism could be understood, then more attractive metal hydrides could be designed. To this end, we conducted Transmission Electron Microscopy (TEM) studies to explain the role of the Ti dopants. The first known thorough particle size analysis of the NaAlH4 system was conducted, as well as TEM-EELS (Electron Energy Loss Spectroscopy), TEM-EDS (Energy Dispersive X-ray Spectroscopy), and in-situ imaging studies. Preparation methods were found to be important for the

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

International Nuclear Information System (INIS)

Carrion, Nereida; Murillo, Miguel; Montiel, Edie; Diaz, Dorfe

2003-01-01

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

Alloys for hydrogen storage in nickel/hydrogen and nickel/metal hydride batteries

Science.gov (United States)

Anani, Anaba; Visintin, Arnaldo; Petrov, Konstantin; Srinivasan, Supramaniam; Reilly, James J.; Johnson, John R.; Schwarz, Ricardo B.; Desch, Paul B.

1993-01-01

Since 1990, there has been an ongoing collaboration among the authors in the three laboratories to (1) prepare alloys of the AB(sub 5) and AB(sub 2) types, using arc-melting/annealing and mechanical alloying/annealing techniques; (2) examine their physico-chemical characteristics (morphology, composition); (3) determine the hydrogen absorption/desorption behavior (pressure-composition isotherms as a function of temperature); and (4) evaluate their performance characteristics as hydride electrodes (charge/discharge, capacity retention, cycle life, high rate capability). The work carried out on representative AB(sub 5) and AB(sub 2) type modified alloys (by partial substitution or with small additives of other elements) is presented. The purpose of the modification was to optimize the thermodynamics and kinetics of the hydriding/dehydriding reactions and enhance the stabilities of the alloys for the desired battery applications. The results of our collaboration, to date, demonstrate that (1) alloys prepared by arc melting/annealing and mechanical alloying/annealing techniques exhibit similar morphology, composition and hydriding/dehydriding characteristics; (2) alloys with the appropriate small amounts of substituent or additive elements: (1) retain the single phase structure, (2) improve the hydriding/dehydriding reactions for the battery applications, and (3) enhance the stability in the battery environment; and (3) the AB(sub 2) type alloys exhibit higher energy densities than the AB(sub 5) type alloys but the state-of-the-art, commercialized batteries are predominantly manufactured using Ab(sub 5) type alloys.

Novel metal complexes of mixed piperaquine-acetaminophen and piperaquine-acetylsalicylic acid: Synthesis, characterization and antimicrobial activities

Directory of Open Access Journals (Sweden)

Yusuf Oloruntoyin Ayipo

2016-11-01

Full Text Available Synthesis of coordination compounds of Zinc(II, Copper(II, Nickel(II, Cobalt(II and Iron(II with mixed piperaquine-acetaminophen and piperaquine-acetylsalicylic acid has been studied. The complexes were characterized via: solubility test, melting point determination, conductivity measurement, Atomic Absorption Spectroscopy, UV-Visible Spectroscopy, FTIR Spectroscopy and magnetic susceptibility. The complexes were proposed to have a stoichiometry ratio of 1:1:1 between each metal salt and the ligands with tetrahedral and octahedral geometry following the reaction pattern of MX.yH2O + L1L2/3 to give ML1L2/3X.yH2O. Biological activities of the synthesized complexes have been evaluated against Escherichia coli and Staphylococcus aureus.

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.

Hydrocarbon-soluble calcium hydride: a "worker-bee" in calcium chemistry.

Science.gov (United States)

Spielmann, Jan; Harder, Sjoerd

2007-01-01

The reactivity of the hydrocarbon-soluble calcium hydride complex [{CaH(dipp-nacnac)(thf)}(2)] (1; dipp-nacnac=CH{(CMe)(2,6-iPr(2)C(6)H(3)N)}(2)) with a large variety of substrates has been investigated. Addition of 1 to C=O and C=N functionalities gave easy access to calcium alkoxide and amide complexes. Similarly, reduction of the C[triple chemical bond]N bond in a cyanide or an isocyanide resulted in the first calcium aldimide complexes [Ca{N=C(H)R}(dipp-nacnac)] and [Ca{C(H)=NR}(dipp-nacnac)], respectively. Complexation of 1 with borane or alane Lewis acids gave the borates and alanates as contact ion pairs. In reaction with epoxides, nucleophilic ring-opening is observed as the major reaction. The high reactivity of hydrocarbon-soluble 1 with most functional groups contrasts strongly with that of insoluble CaH(2), which is essentially inert and is used as a common drying agent. Crystal structures of the following products are presented: [{Ca{OC(H)Ph(2)}(dipp-nacnac)}(2)], [{Ca{N=C(H)Ph}(dipp-nacnac)}(2)], [{Ca{C(H)=NC(Me)(2)CH(2)C(Me)(3)}(dipp-nacnac)}(2)], [{Ca{C(H)=NCy}(dipp-nacnac)}(2)], [Ca(dipp-nacnac)(thf)](+)[H(2)BC(8)H(14)](-) and [{Ca(OCy)(dipp-nacnac)}(2)]. The generally smooth and clean conversions of 1 with a variety of substrates and the stability of most intermediates against ligand exchange make 1 a valuable key precursor in the syntheses of a wide variety of beta-diketiminate calcium complexes.

Modifications of the hydriding kinetics of a metallic surface, using ion implantation

International Nuclear Information System (INIS)

Crusset, D.

1992-10-01

Uranium reacts with hydrogen to form an hydride: this reaction leads to the total destruction of the material. To modify the reactivity of an uranium surface towards hydrogen, ion implantation was selected, among surface treatments techniques. Four elements (carbon, nitrogen, oxygen, sulfur) were implanted to different doses. The results show a modification of the hydriding mechanism and a significant increase in the reaction induction times, notably at high implantation doses. Several techniques (SIMS, X-rays phases analysis and residual stresses determination) were used to characterize the samples and understand the different mechanisms involved

Computer simulation of hydrogen diffusion and hydride precipitation at Ta/Zr bond interface. Hydrogen embrittlement in SUS304ULC/Ta/Zr explosive bonded joint

International Nuclear Information System (INIS)

Saida, Kazuyoshi; Fujimoto, Tetsuya; Nishimoto, Kazutoshi

2010-01-01

The concentration of hydrogen and precipitation of zirconium hydrides in Ta/Zr explosive bonded joint were analysed by computer simulation. Numerical model of hydride precipitation under hydrogen diffusion was simplified by the alternate model coupled the macroscopic hydrogen diffusion with the microscopic hydride precipitation. Effects of the initial hydrogen content in Ta, working degree of Zr and post-bond heat treatment on the hydrogen diffusion and hydride precipitation were investigated. Hydrogen was rapidly diffused from Ta substrate into Zr after explosive bonding and temporarily concentrated at Ta/Zr bond interface. Zirconium hydrides were precipitated and grew at Ta/Zr bond interface, and the precipitation zone of hydrides was enlarged with the lapse of time. The precipitation of zirconium hydrides was promoted when the initial hydrogen content in Ta and working degree of Zr were increased. The concentration of hydrogen and precipitation of hydrides at the bond interface were reduced and diminished by post-bond heat treatment at 373 K. It was deduced that hydrogen embrittlement in Ta/Zr explosive bonded joint was caused by the precipitation of zirconium hydrides and concentration of hydrogen at Ta/Zr bond interface during the diffusion of hydrogen containing in Ta substrate. (author)

Effect of magnesium hydride on the corrosion behavior of an AZ91 magnesium alloy in sodium chloride solution

International Nuclear Information System (INIS)

Chen Jian; Dong Junhua; Wang Jianqiu; Han Enhou; Ke Wei

2008-01-01

The effect of magnesium hydride on the corrosion behavior of an as-cast AZ91 alloy in 3.5 wt.% NaCl solution was investigated using gas collection method and potentiostatic test. The Pourbaix diagram of Mg-H 2 O system was built using thermodynamic calculation. It was possible that magnesium hydride could form in the whole pH range in theory. The experimental results showed that at cathodic region, magnesium hydride formed on surface, which was the controlling process for the corrosion behavior of AZ91 alloy; at anodic region and free corrosion potential, magnesium hydride model and partially protective film model, monovalent magnesium ion model and particle undermining model were responsible for the corrosion process of AZ91 alloy

Flow injection electrochemical hydride generation inductively coupled plasma time-of-flight mass spectrometry for the simultaneous determination of hydride forming elements and its application to the analysis of fresh water samples

International Nuclear Information System (INIS)

Bings, Nicolas H.; Stefanka, Zsolt; Mallada, Sergio Rodriguez

2003-01-01

A flow injection (FI) method was developed using electrochemical hydride generation (EcHG) as a sample introduction system, coupled to an inductively coupled plasma time-of-flight mass spectrometer (ICP-TOFMS) for rapid and simultaneous determination of six elements forming hydrides (As, Bi, Ge, Hg, Sb and Se). A novel low volume electrolysis cell, especially suited for FI experiments was designed and the conditions for simultaneous electrochemical hydride generation (EcHG; electrolyte concentrations and flow rates, electrolysis voltage and current) as well as the ICP-TOFMS operational parameters (carrier gas flow rate, modulation pulse width (MPW)) for the simultaneous determination of 12 isotopes were optimized. The compromise operation parameters of the electrolysis were found to be 1.4 and 3 ml min -1 for the anolyte and catholyte flow rates, respectively, using 2 M sulphuric acid. An optimum electrolysis current of 0.7 A (16 V) and an argon carrier gas flow rate of 0.91 l min -1 were chosen. A modulation pulse width of 5 μs, which influences the sensitivity through the amount of ions being collected by the MS per single analytical cycle, provided optimum results for the detection of transient signals. The achieved detection limits were compared with those obtained by using FI in combination with conventional nebulization (FI-ICP-TOFMS); values for chemical hydride generation (FI-CHG-ICP-TOFMS) were taken from the literature. By using a 200 μl sample loop absolute detection limits (3σ) in the range of 10-160 pg for As, Bi, Ge, Hg, Sb and 1.1 ng for Se and a precision of 4-8% for seven replicate injections of 20-100 ng ml -1 multielemental sample solutions were achieved. The analysis of a standard reference material (SRM) 1643d (NIST, 'Trace Elements in Water') showed good agreement with the certified values for As and Sb. Se showed a drastic difference, which is probably due to the presence of hydride-inactive Se species in the sample. Recoveries better than

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)

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

U-Mo Alloy Powder Obtained Through Selective Hydriding. Particle Size Control

International Nuclear Information System (INIS)

Balart, S.N.; Bruzzoni, P.; Granovsky, M.S.

2002-01-01

Hydride-dehydride methods to obtain U-Mo alloy powder for high-density fuel elements have been successfully tested by different authors. One of these methods is the selective hydriding of the α phase (HSα). In the HSα method, a key step is the partial decomposition of the γ phase (retained by quenching) to α phase and an enriched γ phase or U 2 Mo. This transformation starts mainly at grain boundaries. Subsequent hydrogenation of this material leads to selective hydriding of the α phase, embrittlement and intergranular fracture. According to this picture, the particle size of the final product should be related to the γ grain size of the starting alloy. The feasibility of controlling the particle size of the product by changing the γ grain size of the starting alloy is currently investigated. In this work an U-7 wt% Mo alloy was subjected to various heat treatments in order to obtain different grain sizes. The results on the powder particle size distribution after applying the HSα method to these samples show that there is a strong correlation between the original γ grain size and the particle size distribution of the powder. (author)

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

Vanadium-based alloy hydrides for heat pumps, compressors, and isotope separation

International Nuclear Information System (INIS)

Libowitz, G.G.

1988-01-01

A series of body-centered cubic (b.c.c.) solid solution alloys have been developed which appears to be unusually suitable for several applications involving metal hydrides. It is normally very difficult to induce the body-centered cubic metals, Nb, V, and Ta, to react with hydrogen; in bulk form the reaction will simply not occur at room temperature. Alloys containing Nb exhibited very large hysteresis effects on hydride formation and thus are not suitable for most applications. However, the V-Ti based alloys showed relatively little hysteresis, and because of their unusual thermodynamic properties offer significant advantages for the specific applications discussed below. (orig./HB)

Hydrogen storage properties of Mg-23.3wt.%Ni eutectic alloy prepared via hydriding combustion synthesis followed by mechanical milling

International Nuclear Information System (INIS)

Liquan Li; Yunfeng Zhu; Xiaofeng Liu

2006-01-01

A Mg-23.3wt.%Ni eutectic alloy was prepared by the process of hydriding combustion synthesis followed by mechanical milling (HCS+MM). The product showed a high hydriding rate at 373 K and the dehydrogenation started at temperature as low as 423 K. Several reasons contributing to the improvement in hydrogen storage properties were presented. The result of this study will provide attractive information for mobile applications of magnesium hydrogen storage materials, and the process of HCS+MM developed in this study showed its potential for synthesizing magnesium based hydrogen storage materials with novel hydriding/de-hydriding properties. (authors)

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

International Nuclear Information System (INIS)

Surrey, Alexander; Schultz, Ludwig; Rellinghaus, Bernd

2017-01-01

Highlights: • Multislice HRTEM contrast simulations of a windowed environmental cell. • Study of Mg and MgH2 nanocrystals as model system in hydrogen at ambient pressure. • Investigation of spatial resolution and contrast depending on specimen thickness, defocus, and hydrogen pressure. • Atomic resolution is expected for specimens as thin as 5  nm. - Abstract: The use of transmission electron microscopy (TEM) for the structural characterization of many nanostructured hydrides, which are relevant for solid state hydrogen storage, is hindered due to a rapid decomposition of the specimen upon irradiation with the electron beam. Environmental TEM allows to stabilize the hydrides by applying a hydrogen back pressure of up to 4.5 bar in a windowed environmental cell. The feasibility of high-resolution TEM (HRTEM) investigations of light weight metals and metal hydrides in such a “nanoreactor” is studied theoretically by means of multislice HRTEM contrast simulations using Mg and its hydride phase, MgH_2, as model system. Such a setup provides the general opportunity to study dehydrogenation and hydrogenation reactions at the nanoscale under technological application conditions. We analyze the dependence of both the spatial resolution and the HRTEM image contrast on parameters such as the defocus, the metal/hydride thickness, and the hydrogen pressure in order to explore the possibilities and limitations of in-situ experiments with windowed environmental cells. Such simulations may be highly valuable to pre-evaluate future experimental studies.

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

Energy Technology Data Exchange (ETDEWEB)

Surrey, Alexander, E-mail: a.surrey@ifw-dresden.de [IFW Dresden, Institute for Metallic Materials, P.O. Box 270116, D-01171 Dresden (Germany); Institut für Festkörperphysik, Technische Universität Dresden, D-01062 Dresden (Germany); Schultz, Ludwig [IFW Dresden, Institute for Metallic Materials, P.O. Box 270116, D-01171 Dresden (Germany); Institut für Festkörperphysik, Technische Universität Dresden, D-01062 Dresden (Germany); Rellinghaus, Bernd, E-mail: b.rellinghaus@ifw-dresden.de [IFW Dresden, Institute for Metallic Materials, P.O. Box 270116, D-01171 Dresden (Germany)

2017-04-15

Highlights: • Multislice HRTEM contrast simulations of a windowed environmental cell. • Study of Mg and MgH2 nanocrystals as model system in hydrogen at ambient pressure. • Investigation of spatial resolution and contrast depending on specimen thickness, defocus, and hydrogen pressure. • Atomic resolution is expected for specimens as thin as 5  nm. - Abstract: The use of transmission electron microscopy (TEM) for the structural characterization of many nanostructured hydrides, which are relevant for solid state hydrogen storage, is hindered due to a rapid decomposition of the specimen upon irradiation with the electron beam. Environmental TEM allows to stabilize the hydrides by applying a hydrogen back pressure of up to 4.5 bar in a windowed environmental cell. The feasibility of high-resolution TEM (HRTEM) investigations of light weight metals and metal hydrides in such a “nanoreactor” is studied theoretically by means of multislice HRTEM contrast simulations using Mg and its hydride phase, MgH{sub 2}, as model system. Such a setup provides the general opportunity to study dehydrogenation and hydrogenation reactions at the nanoscale under technological application conditions. We analyze the dependence of both the spatial resolution and the HRTEM image contrast on parameters such as the defocus, the metal/hydride thickness, and the hydrogen pressure in order to explore the possibilities and limitations of in-situ experiments with windowed environmental cells. Such simulations may be highly valuable to pre-evaluate future experimental studies.

Behavior and failure of fresh, hydrided and irradiated Zircaloy-4 fuel claddings under RIA conditions

International Nuclear Information System (INIS)

Le Saux, M.

2008-01-01

The purpose of this study is to characterize and simulate the mechanical behaviour and failure of fresh, hydrided and irradiated (in pressurized water reactors) cold-worked stress relieved Zircaloy-4 fuel claddings under reactivity initiated accident conditions. A model is proposed to describe the anisotropic viscoplastic mechanical behavior of the material as a function of temperature (from 20 C up to 1100 C), strain rate (from 3.10 -4 s -1 up to 5 s -1 ), fluence (from 0 up to 1026 n.m -2 ) and irradiation conditions. Axial tensile, hoop tensile, expansion due to compression and hoop plane strain tensile tests are performed at 25 C, 350 C and 480 C in order to analyse the anisotropic plastic and failure properties of the non-irradiated material hydrided up to 1200 ppm. Material strength and strain hardening depend on temperature and hydrogen in solid solution and precipitated hydride contents. Plastic anisotropy is not significantly modified by hydrogen. The material is embrittled by hydrides at room temperature. The plastic strain that leads to hydride cracking decreases with increasing hydrogen content. The material ductility, which increases with increasing temperature, is not deteriorated by hydrogen at 350 C and 480 C. Macroscopic fracture modes and damage mechanisms depend on specimen geometry, temperature and hydrogen content. A Gurson type model is finally proposed to describe both the anisotropic viscoplastic behavior and the ductile fracture of the material as a function of temperature and hydrogen content. (author) [fr

White Paper Summary of 2nd ASTM International Workshop on Hydrides in Zirconium Alloy Cladding

Energy Technology Data Exchange (ETDEWEB)

Sindelar, R. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Louthan, M. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); PNNL, B. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

2015-05-29

This white paper recommends that ASTM International develop standards to address the potential impact of hydrides on the long term performance of irradiated zirconium alloys. The need for such standards was apparent during the 2nd ASTM International Workshop on Hydrides in Zirconium Alloy Cladding and Assembly Components, sponsored by ASTM International Committee C26.13 and held on June 10-12, 2014, in Jackson, Wyoming. The potentially adverse impacts of hydrogen and hydrides on the long term performance of irradiated zirconium-alloy cladding on used fuel were shown to depend on multiple factors such as alloy chemistry and processing, irradiation and post irradiation history, residual and applied stresses and stress states, and the service environment. These factors determine the hydrogen content and hydride morphology in the alloy, which, in turn, influence the response of the alloy to the thermo-mechanical conditions imposed (and anticipated) during storage, transport and disposal of used nuclear fuel. Workshop presentations and discussions showed that although hydrogen/hydride induced degradation of zirconium alloys may be of concern, the potential for occurrence and the extent of anticipated degradation vary throughout the nuclear industry because of the variations in hydrogen content, hydride morphology, alloy chemistry and irradiation conditions. The tools and techniques used to characterize hydrides and hydride morphologies and their impacts on material performance also vary. Such variations make site-to-site comparisons of test results and observations difficult. There is no consensus that a single material or system characteristic (e.g., reactor type, burnup, hydrogen content, end-of life stress, alloy type, drying temperature, etc.) is an effective predictor of material response during long term storage or of performance after long term storage. Multi-variable correlations made for one alloy may not represent the behavior of another alloy exposed to

How to Analyse Metal Hydride Decomposition Temperatures Using a Sieverts’ Type Hydriding-Dehydriding Apparatus and Hydrogen-Storage Characteristics for an MgH2–Based Alloy

Directory of Open Access Journals (Sweden)

Young Jun KWAK

2018-02-01

Full Text Available In this work, a method to analyze metal hydride decomposition temperatures (the onset temperature of the metal hydride decomposition and the temperature for the maximum ratio of released gas quantity change with temperature change, of prepared samples were investigated using a Sieverts’ type hydriding-dehydriding apparatus, in which a back-pressure regulator was employed. The quantity of the gas released under 1.0 bar H2 was measured as the temperature was increased with a heating rate of 4 K/min. The variation in the ratio of released hydrogen quantity Hd change with temperature T change, dHd/dT, as a function of temperature was obtained and from the variation in dHd/dT with T, the metal hydride decomposition temperatures were analyzed. This analysis method can be used instead of thermal analysis methods such as thermogravimetric analysis (TGA, differential scanning calorimetry (DSC analysis, differential thermal analysis (DTA, and thermal desorption spectroscopy (TDS analysis. For this analysis, a sample with a composition of 89 wt.% MgH2 + 4.9 wt.% Ni + 1.7 wt.% Zn(BH42 + 1.0 wt% NaCl + 1.7 wt.% Ti + 1.7 wt % Fe (named MgH2-Ni-Zn(BH42-NaCl-Ti-Fe sample was prepared by planetary ball milling. In the prepared MgH2-Ni-Zn(BH42-NaCl-Ti-Fe sample, it is believed that MgH2 begins to decompose at about 575 K and dHd/dT reaches its peak at about 610 K.DOI: http://dx.doi.org/10.5755/j01.ms.24.1.17664

Fast, quantitative, and nondestructive evaluation of hydrided LWR fuel cladding by small angle incoherent neutron scattering of hydrogen

Energy Technology Data Exchange (ETDEWEB)

Yan, Y.; Qian, S.; Littrell, K.; Parish, C.M. [Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Plummer, L.K. [University of Oregon, Eugene, OR 97403 (United States)

2015-05-15

A nondestructive neutron scattering method to precisely measure the uptake of hydrogen and the distribution of hydride precipitates in light water reactor (LWR) fuel cladding was developed. Zircaloy-4 cladding used in commercial LWRs was used to produce hydrided specimens. The hydriding apparatus consists of a closed stainless-steel vessel that contains Zr alloy specimens and hydrogen gas. Following hydrogen charging, the hydrogen content of the hydrided specimens was measured using the vacuum hot extraction method, by which the samples with desired hydrogen concentrations were selected for the neutron study. Optical microscopy shows that our hydriding procedure results in uniform distribution of circumferential hydrides across the wall thickness. Small angle neutron incoherent scattering was performed in the High Flux Isotope Reactor at Oak Ridge National Laboratory. Our study demonstrates that the hydrogen in commercial Zircaloy-4 cladding can be measured very accurately in minutes by this nondestructive method over a wide range of hydrogen concentrations from a very small amount (≈20 ppm) to over 1000 ppm. The hydrogen distribution in a tube sample was obtained by scaling the neutron scattering rate with a factor determined by a calibration process using standard, destructive direct chemical analysis methods on the specimens. This scale factor can be used in future tests with unknown hydrogen concentrations, thus providing a nondestructive method for determining absolute hydrogen concentrations.

Point defect dynamics in sodium aluminum hydrides - a combined quasielastic neutron scattering and density functional theory study

DEFF Research Database (Denmark)

Shi, Qing; Voss, Johannes; Jacobsen, H.S.

2007-01-01

we study hydrogen dynamics in undoped and TiCl3-doped samples of NaAlH4 and Na3AlH6 using a combination of density functional theory calculations and quasielastic neutron scattering. Hydrogen dynamics is found to be limited and mediated by hydrogen vacancies in both alanate phases, requiring......Understanding the catalytic role of titanium-based additives on the reversible hydrogenation of complex metal hydrides is an essential step towards developing hydrogen storage materials for the transport sector. Improved bulk diffusion of hydrogen is one of the proposed catalytic effects, and here...

Synthesis of Fe–Li–Cr Multinuclear Complexes as Molecular Magnet Materials

Directory of Open Access Journals (Sweden)

Iis Siti Jahro

2008-03-01

Full Text Available Multinuclear complexes have received considerable interest as molecular magnet materials. Up to now, several complex compounds based on bidentate ligand 2,2’ bipyridine have been synthesized. In this research, the Fe-Li-Cr multinuclear complexes with derivative 2’2- bipyridine ligands: 2-(2’-pyridylquinoline(pq, 2,2’-Pyridil(pdl have been synthesized. The oxalate (ox ligand has also been used as a bridging ligand in these multinuclear complexes. The chemical formula of Li[FeCr(ox2(pq(BF42(H2O2] and [Fe(pdln][LiCr(ox3] complexes have been verified using metal and C, H, N elemental analysis data. The IR spectra in 350 – 4000 cm-1 range exhibit characteristic absorptions, which support the proposed structure of complex. The plausible structure of the compounds has been drawn based on complex formation mechanism. The magnetic susceptibility at room temperature of the pq-complex is about 5.7 BM and of the pdl- complexes are 4.8 and 5.5 BM. These indicated that both spin states of iron(II exist in the multinuclear complexes.

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.

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.

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

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

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

Energy Technology Data Exchange (ETDEWEB)

Filipek, S.M., E-mail: sfilipek@unipress.waw.pl [Institute of High Pressure Physics PAS, ul. Sokolowska 29, 01-142 Warsaw (Poland); Paul-Boncour, V. [ICMPE-CMTR, CNRS-UPEC, 2-8 rue Henri Dunant, 94320 Thiais (France); Liu, R.S. [Department of Chemistry, National Taiwan University, Taipei 106, Taiwan (China); Jacob, I. [Unit Nuclear Eng., Ben Gurion University of the Negev, Beer-Sheva (Israel); Tsutaoka, T. [Dept. of Sci. Educ., Grad. School of Educ., Hiroshima University, Hiroshima (Japan); Budziak, A. [Institute of Nuclear Physics PAS, 31-342 Kraków (Poland); Morawski, A. [Institute of High Pressure Physics PAS, ul. Sokolowska 29, 01-142 Warsaw (Poland); Sugiura, H. [Yokohama City University, 22-2 Seto, Kanazawa-ku, Yokohama 236-0027 (Japan); Zachariasz, P. [Institute of Electron Technology Cracow Division, ul. Zablocie 39, 30-701 Krakow (Poland); Dybko, K. [Institute of Physics, PAS, 02-668 Warsaw (Poland); Diduszko, R. [Tele and Radio Research Institute, ul. Ratuszowa 11, Warsaw (Poland)

2016-12-01

Brief summary of our former work on high hydrogen pressure syntheses of novel hydrides and studies of their properties is supplemented with new results. Syntheses and properties of a number of hydrides (unstable, metastable or stable in ambient conditions) derived under high hydrogen pressure from intermetallic compounds, like MeT{sub 2}, MeNi{sub 5}, Me{sub 7}T{sub 3}, Y{sub 6}Mn{sub 23} and YMn{sub 12} (where Me = zirconium, yttrium or rare earth; T = transition metal) are presented. Stabilization of ZrFe{sub 2}H{sub 4} due to surface phenomena was revealed. Unusual role of manganese in hydride forming processes is pointed out. Hydrogen induced phase transitions, suppression of magnetism, antiferromagnetic-ferromagnetic and metal-insulator or semimetal-metal transitions are described. Equations of state (EOS) of hydrides submitted to hydrostatic pressures up to 30 GPa are presented and discussed.

CO2 activation through silylimido and silylamido zirconium hydrides supported on N-donor chelating SBA15 surface ligand

KAUST Repository

Pasha, Fahran Ahmad

2016-01-04

Density functional theory calculations and 2D 1H-13C HETCOR solid state NMR spectroscopy prove that CO2 can probe, by its own reactivity, different types of N-donor surface ligands on SBA15-supported ZrIV hydrides: [(≡Si-O-)(≡Si-N=)[Zr]H] and [(≡Si-NH-)(≡Si-X-)[Zr]H2] (X = O or NH). Moreover, [(≡Si-O-)(≡Si-N=)[Zr]H] activates CO2 more efficiently than the other complexes and leads to a carbimato Zr formate.

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

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

Directory of Open Access Journals (Sweden)

Chi-Chang Wang

2014-05-01

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

Titanium tritide radioisotope heat source development: palladium-coated titanium hydriding kinetics and tritium loading tests

International Nuclear Information System (INIS)

Van Blarigan, Peter; Shugard, Andrew D.; Walters, R. Tom

2012-01-01

We have found that a 180 nm palladium coating enables titanium to be loaded with hydrogen isotopes without the typical 400-500 C vacuum activation step. The hydriding kinetics of Pd coated Ti can be described by the Mintz-Bloch adherent film model, where the rate of hydrogen absorption is controlled by diffusion through an adherent metal-hydride layer. Hydriding rate constants of Pd coated and vacuum activated Ti were found to be very similar. In addition, deuterium/tritium loading experiments were done on stacks of Pd coated Ti foil in a representative-size radioisotope heat source vessel. The experiments demonstrated that such a vessel could be loaded completely, at temperatures below 300 C, in less than 10 hours, using existing department-of-energy tritium handling infrastructure.

An Investigation on the Persistence of Uranium Hydride during Storage of Simulant Nuclear Waste Packages.

Science.gov (United States)

Stitt, C A; Harker, N J; Hallam, K R; Paraskevoulakos, C; Banos, A; Rennie, S; Jowsey, J; Scott, T B

2015-01-01

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 reactant in an anoxic water system, but without encapsulation in grout. This was attributed to the grout acting as a physical barrier limiting the access of oxidising species to the uranium surface. Uranium hydride was observed to persist throughout the 10 month storage period and industrial consequences of this observed persistence are discussed.

Topotactic Solid-State Metal Hydride Reductions of Sr2MnO4.

Science.gov (United States)

Hernden, Bradley C; Lussier, Joey A; Bieringer, Mario

2015-05-04

We report novel details regarding the reactivity and mechanism of the solid-state topotactic reduction of Sr2MnO4 using a series of solid-state metal hydrides. Comprehensive details describing the active reducing species are reported and comments on the reductive mechanism are provided, where it is shown that more than one electron is being donated by H(-). Commonly used solid-state hydrides LiH, NaH, and CaH2, were characterized in terms of reducing power. In addition the unexplored solid-state hydrides MgH2, SrH2, and BaH2 are evaluated as potential solid-state reductants and characterized in terms of their reductive reactivities. These 6 group I and II metal hydrides show the following trend in terms of reactivity: MgH2 < SrH2 < LiH ≈ CaH2 ≈ BaH2 < NaH. The order of the reductants are discussed in terms of metal electronegativity and bond strengths. NaH and the novel use of SrH2 allowed for targeted synthesis of reduced Sr2MnO(4-x) (0 ≤ x ≤ 0.37) phases. The enhanced control during synthesis demonstrated by this soft chemistry approach has allowed for a more comprehensive and systematic evaluation of Sr2MnO(4-x) phases than previously reported phases prepared by high temperature methods. Sr2MnO3.63(1) has for the first time been shown to be monoclinic by powder X-ray diffraction and the oxidative monoclinic to tetragonal transition occurs at 450 °C.

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

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.

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.

Development of metal complexes which has a novel type of dhotocatalysis activity; Shinki hikari shokubai tokusei wo yusuru kinzoku sakutai no sousei

Energy Technology Data Exchange (ETDEWEB)

Ishitani, Osamu [Saitama University, Saitama (Japan). Graduate School of Sceince and Engineering

1999-12-16

Purpose of this research are (1) development of photocatalysts which selectively drive hydride transfer and (2) their application to the enantioselective reduction of an unsaturated substrate. photocatalysis of [Ru(bpy){sub 2}(py){sub 2}]{sup 2+} (1) and [Ru(tpy)(bpy)(py)]{sup 2+} (2) (bpy=2,2'-bipyridine, tpy=2,2' : 6',2' '-terpyridine, py=pyridine) for reduction of unsaturated compounds was investigated using triethylamine as a reductant. Formation of the hydrogenated compounds was observed but the corresponding one electron reduced compounds were not detected at all. The complex 1 photocatalysed the reduction of trifluoroacetophenone (5) and gave the alcohol in a 67% yield but 2 gave only a 27% yield. The reaction proceeds via the photosubstitution of a py ligand of the ruthenium complex, followed by photochemical formation of the hydride complex. The ruthenium hydride complex reacts with 5 to give [Ru(tpy)(bpy)(OCHPhCF{sub 3})]{sup +} (4). Dissociation of 4 to the alcohol was not efficient and the yield was 10%. (author)

Sulphonated metal phthalocyanine complexes as redox indicators in micro titrations with cerium(IV) sulphate

Energy Technology Data Exchange (ETDEWEB)

Gowda, H S; Achar, B N [Mysore Univ. (India). Dept. of Chemistry

1980-01-01

Tetrasodium salts of copper(II) 4,4', 4'', 4'''-tetrasulphophthalocyanine 2-hydrate, nickel(II) 4,4', 4'', 4'''-tetrasulphophthalocyanine, nickel(II) 3,3', 3'', 3'''-tetrasulphophthalocyanine and cobalt(II) 4,4', 4'', 4'''-tetrasulphophthalocyanine 2-hydrate, and copper phthalocyanine trisulphonic acid are prepared in pure state. The molar absorptivity and formal redox potentials of the complexes are determined. The complexes are proposed as sensitive redox indicators in the micro determination of iron(II), arsenic(III), molybdenum(V), uranium(IV) and hydroquinone with 0.001-0.0005N cerium(IV) sulphate in sulphuric, hydrochloric and acetic acid media. They give sharp colour change from light turquoise blue to pale purple colour at the equivalence point. They have advantages over a few existing redox indicators.