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Sample records for actinium hydrides

  1. Interstellar Hydrides

    CERN Document Server

    Gerin, Maryvonne; Goicoechea, Javier R

    2016-01-01

    Interstellar hydrides -- that is, molecules containing a single heavy element atom with one or more hydrogen atoms -- were among the first molecules detected outside the solar system. They lie at the root of interstellar chemistry, being among the first species to form in initially-atomic gas, along with molecular hydrogen and its associated ions. Because the chemical pathways leading to the formation of interstellar hydrides are relatively simple, the analysis of the observed abundances is relatively straightforward and provides key information about the environments where hydrides are found. Recent years have seen rapid progress in our understanding of interstellar hydrides, thanks largely to far-IR and submillimeter observations performed with the Herschel Space Observatory. In this review, we will discuss observations of interstellar hydrides, along with the advanced modeling approaches that have been used to interpret them, and the unique information that has thereby been obtained.

  2. Spectroscopic and computational investigation of actinium coordination chemistry

    Science.gov (United States)

    Ferrier, Maryline G.; Batista, Enrique R.; Berg, John M.; Birnbaum, Eva R.; Cross, Justin N.; Engle, Jonathan W.; La Pierre, Henry S.; Kozimor, Stosh A.; Lezama Pacheco, Juan S.; Stein, Benjamin W.; Stieber, S. Chantal E.; Wilson, Justin J.

    2016-08-01

    Actinium-225 is a promising isotope for targeted-α therapy. Unfortunately, progress in developing chelators for medicinal applications has been hindered by a limited understanding of actinium chemistry. This knowledge gap is primarily associated with handling actinium, as it is highly radioactive and in short supply. Hence, AcIII reactivity is often inferred from the lanthanides and minor actinides (that is, Am, Cm), with limited success. Here we overcome these challenges and characterize actinium in HCl solutions using X-ray absorption spectroscopy and molecular dynamics density functional theory. The Ac-Cl and Ac-OH2O distances are measured to be 2.95(3) and 2.59(3) Å, respectively. The X-ray absorption spectroscopy comparisons between AcIII and AmIII in HCl solutions indicate AcIII coordinates more inner-sphere Cl1- ligands (3.2+/-1.1) than AmIII (0.8+/-0.3). These results imply diverse reactivity for the +3 actinides and highlight the unexpected and unique AcIII chemical behaviour.

  3. Separation of Actinium 227 from the uranium minerals

    International Nuclear Information System (INIS)

    The purpose of this work was to separate Actinium 227, whose content is 18%, from the mineral carnotite found in Gomez Chihuahua mountain range in Mexico. The mineral before processing is is pre-concentrated and passed, first through anionic exchange resins, later the eluate obtained is passed through cationic resins. The resins were 20-50 MESH QOWEX and 100-200 MESH 50 X 8-20 in some cased 200-400 MESH AG 50W-X8, 1X8 in other cases. The eluates from the ionic exchange were electrodeposited on stainless steel polished disc cathode and platinum electrode as anode; under a current ODF 10mA for 2.5 to 5 hours and of 100mA for .5 of an hour. it was possible to identify the Actinium 227 by means of its descendents, TH-227 and RA-223, through alpha spectroscopy. Due to the radiochemical purity which the electro deposits were obtained the Actinium 227 was low and was not quantitatively determined. A large majority of the members of the natural radioactive series 3 were identified and even alpha energies reported in the literature with very low percentages of non-identified emissions were observed. We conclude that a more precise study is needed concerning ionic exchange and electrodeposit to obtain an Actinium 227 of radiochemical purity. (Author)

  4. Spectroscopic and computational investigation of actinium coordination chemistry

    Science.gov (United States)

    Ferrier, Maryline G.; Batista, Enrique R.; Berg, John M.; Birnbaum, Eva R.; Cross, Justin N.; Engle, Jonathan W.; La Pierre, Henry S.; Kozimor, Stosh A.; Lezama Pacheco, Juan S.; Stein, Benjamin W.; Stieber, S. Chantal E.; Wilson, Justin J.

    2016-01-01

    Actinium-225 is a promising isotope for targeted-α therapy. Unfortunately, progress in developing chelators for medicinal applications has been hindered by a limited understanding of actinium chemistry. This knowledge gap is primarily associated with handling actinium, as it is highly radioactive and in short supply. Hence, AcIII reactivity is often inferred from the lanthanides and minor actinides (that is, Am, Cm), with limited success. Here we overcome these challenges and characterize actinium in HCl solutions using X-ray absorption spectroscopy and molecular dynamics density functional theory. The Ac–Cl and Ac–OH2O distances are measured to be 2.95(3) and 2.59(3) Å, respectively. The X-ray absorption spectroscopy comparisons between AcIII and AmIII in HCl solutions indicate AcIII coordinates more inner-sphere Cl1– ligands (3.2±1.1) than AmIII (0.8±0.3). These results imply diverse reactivity for the +3 actinides and highlight the unexpected and unique AcIII chemical behaviour. PMID:27531582

  5. Discovery of the actinium, thorium, protactinium, and uranium isotopes

    CERN Document Server

    Fry, C

    2012-01-01

    Currently, 31 actinium, 31 thorium, 28 protactinium, and 23 uranium isotopes have so far been observed; the discovery of these isotopes is discussed. For each isotope a brief summary of the first refereed publication, including the production and identification method, is presented.

  6. Spectroscopic and computational investigation of actinium coordination chemistry.

    Science.gov (United States)

    Ferrier, Maryline G; Batista, Enrique R; Berg, John M; Birnbaum, Eva R; Cross, Justin N; Engle, Jonathan W; La Pierre, Henry S; Kozimor, Stosh A; Lezama Pacheco, Juan S; Stein, Benjamin W; Stieber, S Chantal E; Wilson, Justin J

    2016-01-01

    Actinium-225 is a promising isotope for targeted-α therapy. Unfortunately, progress in developing chelators for medicinal applications has been hindered by a limited understanding of actinium chemistry. This knowledge gap is primarily associated with handling actinium, as it is highly radioactive and in short supply. Hence, Ac(III) reactivity is often inferred from the lanthanides and minor actinides (that is, Am, Cm), with limited success. Here we overcome these challenges and characterize actinium in HCl solutions using X-ray absorption spectroscopy and molecular dynamics density functional theory. The Ac-Cl and Ac-OH2O distances are measured to be 2.95(3) and 2.59(3) Å, respectively. The X-ray absorption spectroscopy comparisons between Ac(III) and Am(III) in HCl solutions indicate Ac(III) coordinates more inner-sphere Cl(1-) ligands (3.2±1.1) than Am(III) (0.8±0.3). These results imply diverse reactivity for the +3 actinides and highlight the unexpected and unique Ac(III) chemical behaviour. PMID:27531582

  7. Hysteresis in Metal Hydrides.

    Science.gov (United States)

    Flanagan, Ted B., And Others

    1987-01-01

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

  8. Regenerative Hydride Heat Pump

    Science.gov (United States)

    Jones, Jack A.

    1992-01-01

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

  9. Lightweight hydride storage materials

    Energy Technology Data Exchange (ETDEWEB)

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

    1995-09-01

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

  10. Conference 'Chemistry of hydrides' Proceedings

    International Nuclear Information System (INIS)

    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

  11. Production of Actinium-225 via High Energy Proton Induced Spallation of Thorium-232

    International Nuclear Information System (INIS)

    The science of cancer research is currently expanding its use of alpha particle emitting radioisotopes. Coupled with the discovery and proliferation of molecular species that seek out and attach to tumors, new therapy and diagnostics are being developed to enhance the treatment of cancer and other diseases. This latest technology is commonly referred to as Alpha Immunotherapy (AIT). Actinium-225/Bismuth-213 is a parent/daughter alpha-emitting radioisotope pair that is highly sought after because of the potential for treating numerous diseases and its ability to be chemically compatible with many known and widely used carrier molecules (such as monoclonal antibodies and proteins/peptides). Unfortunately, the worldwide supply of actinium-225 is limited to about 1,000mCi annually and most of that is currently spoken for, thus limiting the ability of this radioisotope pair to enter into research and subsequently clinical trials. The route proposed herein utilizes high energy protons to produce actinium-225 via spallation of a thorium-232 target. As part of previous R and D efforts carried out at Argonne National Laboratory recently in support of the proposed US FRIB facility, it was shown that a very effective production mechanism for actinium-225 is spallation of thorium-232 by high energy proton beams. The base-line simulation for the production rate of actinium-225 by this reaction mechanism is 8E12 atoms per second at 200 MeV proton beam energy with 50 g/cm2 thorium target and 100 kW beam power. An irradiation of one actinium-225 half-life (10 days) produces ∼100 Ci of actinium-225. For a given beam current the reaction cross section increases slightly with energy to about 400 MeV and then decreases slightly for beam energies in the several GeV regime. The object of this effort is to refine the simulations at proton beam energies of 400 MeV and above up to about 8 GeV. Once completed, the simulations will be experimentally verified using 400 MeV and 8 GeV protons

  12. Production of Actinium-225 via High Energy Proton Induced Spallation of Thorium-232

    Energy Technology Data Exchange (ETDEWEB)

    Harvey, James T.; Nolen, Jerry; Vandergrift, George; Gomes, Itacil; Kroc, Tom; Horwitz, Phil; McAlister, Dan; Bowers, Del; Sullivan, Vivian; Greene, John

    2011-12-30

    The science of cancer research is currently expanding its use of alpha particle emitting radioisotopes. Coupled with the discovery and proliferation of molecular species that seek out and attach to tumors, new therapy and diagnostics are being developed to enhance the treatment of cancer and other diseases. This latest technology is commonly referred to as Alpha Immunotherapy (AIT). Actinium-225/Bismuth-213 is a parent/daughter alpha-emitting radioisotope pair that is highly sought after because of the potential for treating numerous diseases and its ability to be chemically compatible with many known and widely used carrier molecules (such as monoclonal antibodies and proteins/peptides). Unfortunately, the worldwide supply of actinium-225 is limited to about 1,000mCi annually and most of that is currently spoken for, thus limiting the ability of this radioisotope pair to enter into research and subsequently clinical trials. The route proposed herein utilizes high energy protons to produce actinium-225 via spallation of a thorium-232 target. As part of previous R and D efforts carried out at Argonne National Laboratory recently in support of the proposed US FRIB facility, it was shown that a very effective production mechanism for actinium-225 is spallation of thorium-232 by high energy proton beams. The base-line simulation for the production rate of actinium-225 by this reaction mechanism is 8E12 atoms per second at 200 MeV proton beam energy with 50 g/cm2 thorium target and 100 kW beam power. An irradiation of one actinium-225 half-life (10 days) produces {approx}100 Ci of actinium-225. For a given beam current the reaction cross section increases slightly with energy to about 400 MeV and then decreases slightly for beam energies in the several GeV regime. The object of this effort is to refine the simulations at proton beam energies of 400 MeV and above up to about 8 GeV. Once completed, the simulations will be experimentally verified using 400 MeV and 8 Ge

  13. 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.)

  14. Erbium hydride decomposition kinetics.

    Energy Technology Data Exchange (ETDEWEB)

    Ferrizz, Robert Matthew

    2006-11-01

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

  15. Metal hydride air conditioner

    Institute of Scientific and Technical Information of China (English)

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

    2005-01-01

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

  16. Hydride development for hydrogen storage

    Energy Technology Data Exchange (ETDEWEB)

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

    1996-10-01

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

  17. Geoneutrino and Hydridic Earth model

    CERN Document Server

    Bezrukov, Leonid

    2013-01-01

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

  18. Physics of hydride fueled PWR

    Science.gov (United States)

    Ganda, Francesco

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

  19. A New Reducing Regent: Dichloroindium Hydride

    Institute of Scientific and Technical Information of China (English)

    A. BABA; I. SHIBATA; N. HAYASHI

    2005-01-01

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

  20. Hydride Olefin complexes of tantalum and niobium

    NARCIS (Netherlands)

    Klazinga, Aan Hendrik

    1979-01-01

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

  1. Luminescent properties of aluminum hydride

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-10-15

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

  2. Hydrogen, lithium, and lithium hydride production

    Science.gov (United States)

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

    2014-03-25

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

  3. Thermomechanical properties of hafnium hydride

    International Nuclear Information System (INIS)

    Fine bulk samples of delta-phase Hf hydride with various hydrogen contents (CH) ranging from 1.62 to 1.72 in the atomic ratio (H/Hf) were prepared, and their thermomechanical properties were characterized. At room temperature, the sound velocity and Vickers hardness were measured. The elastic modulus was calculated from the measured sound velocity. In the temperature range from room temperature to 673 K, the thermal expansion was measured by using a dilatometer, and the linear thermal expansion coefficient was calculated. Empirical equations describing the thermomechanical properties of Hf hydride as a function of CH were proposed. (author)

  4. Analysis of the gamma spectra of the uranium, actinium, and thorium decay series

    International Nuclear Information System (INIS)

    This report describes the identification of radionuclides in the uranium, actinium, and thorium series by analysis of gamma spectra in the energy range of 40 to 1400 keV. Energies and absolute efficiencies for each gamma line were measured by means of a high-resolution germanium detector and compared with those in the literature. A gamma spectroscopy method, which utilizes an on-line computer for deconvolution of spectra, search and identification of each line, and estimation of activity for each radionuclide, was used to analyze soil and uranium tailings, and ore

  5. 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...... was developed. The parameters milling time, milling intensity, number of balls and form of the alloying metals were investigated. Based on this a final alloying technique for the subsequent preparation of electrode materials was established. The technique comprises milling for 4 hours twice possibly followed...... by annealing at 700°C for 12 hours. The alloys appeared to be nanocrystalline with an average crystallite size around 10 nm before annealing. Special steel containers was developed for the annealing of the metal powders in inert atmosphere. The use of various annealing temperatures was investigated...

  6. Nanostructured, complex hydride systems for hydrogen generation

    Directory of Open Access Journals (Sweden)

    Robert A. Varin

    2015-02-01

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

  7. Inhibited solid propellant composition containing beryllium hydride

    Science.gov (United States)

    Thompson, W. W. (Inventor)

    1978-01-01

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

  8. Crystal structure of gold hydride

    International Nuclear Information System (INIS)

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

  9. Crystal structure of gold hydride

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-10-05

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

  10. Research on Metal Hydride Compressor System

    Institute of Scientific and Technical Information of China (English)

    1999-01-01

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

  11. 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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-07-15

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

  13. Predicting formation enthalpies of metal hydrides

    DEFF Research Database (Denmark)

    Andreasen, A.

    2004-01-01

    In order for the hydrogen based society viz. a society in which hydrogen is the primary energy carrier to become realizable an efficient way of storing hydrogen is required. For this purpose metal hydrides are serious candidates. Metal hydrides are formedby chemical reaction between hydrogen and ...

  14. Submillimeter Spectroscopy of Hydride Molecules

    Science.gov (United States)

    Phillips, T. G.

    1998-05-01

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

  15. Hydrogen-storing hydride complexes

    Science.gov (United States)

    Srinivasan, Sesha S.; Niemann, Michael U.; Goswami, D. Yogi; Stefanakos, Elias K.

    2012-04-10

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

  16. 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.

  17. Experimental reproducibility analysis in DU hydriding

    Energy Technology Data Exchange (ETDEWEB)

    Koo, Daeseo; Park, Jongcheol; Chung, Hongsuk [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2014-10-15

    A storage and delivery system (SDS) is used for storing hydrogen isotopes as a metal hydride form. The rapid hydriding of tritium is very important not only for safety reasons but also for the economic design and operation of the SDS. For the storage, supply, and recovery of hydrogen isotopes, depleted uranium (DU) has been extensively proposed. To develop nuclear fusion technology, it will be necessary to store and supply hydrogen isotopes needed for Tokamak operation. The experimental reproducibility of bed temperature on DU hydriding was also analyzed. The experimental reproducibility of apparatus was acceptable for all the experiments. The experimental reproducibility of tank pressure on DU hydriding was analyzed. As the hydriding performs, the tank pressure showed decreasing trend. The experimental reproducibility of bed temperature on DU hydriding was also analyzed. As the hydriding performs, the bed temperatures increased up to maximum temperature with exothermic reaction and then they showed decreasing trend. The experimental reproducibility of apparatus was acceptable for all the experiments.

  18. 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...... by a slightly lower equilibrium coverage of H, which is a consequence of the lower heat of adsorption for H on Pd hydride....

  19. 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.

  20. Geoneutrino and Hydridic Earth model. Version 2

    OpenAIRE

    Bezrukov, Leonid

    2013-01-01

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

  1. Atomistic Potentials for Palladium-Silver Hydrides

    OpenAIRE

    Hale, L. M.; Wong, B. M.; Zimmerman, J. A.; Zhou, X.

    2013-01-01

    New EAM potentials for the ternary palladium-silver-hydrogen system are developed by extending a previously developed palladium-hydrogen potential. The ternary potentials accurately capture the heat of mixing and structural properties associated with solid solution alloys of palladium-silver. Stable hydrides are produced with properties that smoothly transition across the compositions. Additions of silver to palladium are predicted to alter the properties of the hydrides by decreasing the mis...

  2. Probing the cerium/cerium hydride interface using nanoindentation

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-10-05

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

  3. Probing the cerium/cerium hydride interface using nanoindentation

    International Nuclear Information System (INIS)

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

  4. Thorium and actinium polyphosphonate compounds as bone-seeking alpha particle-emitting agents.

    Science.gov (United States)

    Henriksen, Gjermund; Bruland, Oyvind S; Larsen, Roy H

    2004-01-01

    The present study explores the use of alpha-particle-emitting, bone-seeking agents as candidates for targeted radiotherapy. Actinium and thorium 1,4,7,10 tetraazacyclododecane N,N',N'',N''' 1,4,7,10-tetra(methylene) phosphonic acid (DOTMP) and thorium-diethylene triamine N,N',N'' penta(methylene) phosphonic acid (DTMP) were prepared and their biodistribution evaluated in conventional Balb/C mice at four hours after injection. All three bone-seeking agents showed a high uptake in bone and a low uptake in soft tissues. Among the soft tissue organs, only kidney had a relatively high uptake. The femur/kidney ratios for 227Th-DTMP, 228-Ac-DOTMP and 227Th-DOTMP were 14.2, 7.6 and 6.0, respectively. A higher liver uptake of 228Ac-DOTMP was seen than for 227Th-DTMP and 227Th-DOTMP. This suggests that some demetallation of the 228Ac-DOTMP complex had occurred. The results indicate that 225Ac-DOTMP, 227Th-DOTMP and 227Th-DTMP have promising properties as potential therapeutic bone-seeking agents.

  5. Developments towards in-gas-jet laser spectroscopy studies of actinium isotopes at LISOL

    Science.gov (United States)

    Raeder, S.; Bastin, B.; Block, M.; Creemers, P.; Delahaye, P.; Ferrer, R.; Fléchard, X.; Franchoo, S.; Ghys, L.; Gaffney, L. P.; Granados, C.; Heinke, R.; Hijazi, L.; Huyse, M.; Kron, T.; Kudryavtsev, Yu.; Laatiaoui, M.; Lecesne, N.; Luton, F.; Moore, I. D.; Martinez, Y.; Mogilevskiy, E.; Naubereit, P.; Piot, J.; Rothe, S.; Savajols, H.; Sels, S.; Sonnenschein, V.; Traykov, E.; Van Beveren, C.; Van den Bergh, P.; Van Duppen, P.; Wendt, K.; Zadvornaya, A.

    2016-06-01

    To study exotic nuclides at the borders of stability with laser ionization and spectroscopy techniques, highest efficiencies in combination with a high spectral resolution are required. These usually opposing requirements are reconciled by applying the in-gas-laser ionization and spectroscopy (IGLIS) technique in the supersonic gas jet produced by a de Laval nozzle installed at the exit of the stopping gas cell. Carrying out laser ionization in the low-temperature and low density supersonic gas jet eliminates pressure broadening, which will significantly improve the spectral resolution. This article presents the required modifications at the Leuven Isotope Separator On-Line (LISOL) facility that are needed for the first on-line studies of in-gas-jet laser spectroscopy. Different geometries for the gas outlet and extraction ion guides have been tested for their performance regarding the acceptance of laser ionized species as well as for their differential pumping capacities. The specifications and performance of the temporarily installed high repetition rate laser system, including a narrow bandwidth injection-locked Ti:sapphire laser, are discussed and first preliminary results on neutron-deficient actinium isotopes are presented indicating the high capability of this novel technique.

  6. 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...

  7. 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...

  8. 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.

  9. Computational study of metal hydride cooling system

    Energy Technology Data Exchange (ETDEWEB)

    Satheesh, A.; Muthukumar, P.; Dewan, Anupam [Department of Mechanical Engineering, Indian Institute of Technology, Guwahati, Guwahati 781039 (India)

    2009-04-15

    A computational study of a metal hydride cooling system working with MmNi{sub 4.6}Al{sub 0.4}/MmNi{sub 4.6}Fe{sub 0.4} hydride pair is presented. The unsteady, two-dimensional mathematical model in an annular cylindrical configuration is solved numerically for predicting the time dependent conjugate heat and mass transfer characteristics between coupled reactors. The system of equations is solved by the fully implicit finite volume method (FVM). The effects of constant and variable wall temperature boundary conditions on the reaction bed temperature distribution, hydrogen concentration, and equilibrium pressures of the reactors are investigated. A dynamic correlation of the pressure-concentration-temperature plot is presented. At the given operating temperatures of 363/298/278 K (T{sub H}/T{sub M}/T{sub C}), the cycle time for the constant and variable wall temperature boundary conditions of a single-stage and single-effect metal hydride system are found to be 1470.0 s and 1765.6 s, respectively. The computational results are compared with the experimental data reported in the literature for LaNi{sub 4.61}Mn{sub 0.26}Al{sub 0.13}/La{sub 0.6}Y{sub 0.4}Ni{sub 4.8}Mn{sub 0.2} hydride pair and a good agreement between the two was observed. (author)

  10. 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 equ...

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

    International Nuclear Information System (INIS)

    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)

  12. SANS Measurement of Hydrides in Uranium

    International Nuclear Information System (INIS)

    SANS scattering is shown to be an effective method for detecting the presence of hydrogen precipitates in uranium. High purity polycrystalline samples of depleted uranium were given several hydriding treatments which included extended exposures to hydrogen gas at two different pressures at 630 C as well as a furnace anneal at 850 C followed by slow cooling in the near absence hydrogen gas. All samples exhibited neutron scattering that was in proportion to the expected levels of hydrogen content. While the scattering signal was strong, the shape of the scattering curve indicated that the scattering objects were large sized objects. Only by use of a very high angular resolution SANS technique was it possible to make estimates of the major diameter of the scattering objects. This analysis permits an estimate of the volume fraction and means size of the hydride precipitates in uranium

  13. Metal hydrides based high energy density thermal battery

    International Nuclear Information System (INIS)

    Highlights: • The principle of the thermal battery using advanced metal hydrides was demonstrated. • The thermal battery used MgH2 and TiMnV as a working pair. • High energy density can be achieved by the use of MgH2 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 MgH2 as the high temperature hydride material, due to its high energy density and enhanced kinetics; and (2) TiV0.62Mn1.5 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

  14. METHOD AND APPARATUS FOR MAKING URANIUM-HYDRIDE COMPACTS

    Science.gov (United States)

    Wellborn, W.; Armstrong, J.R.

    1959-03-10

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

  15. High energy density battery based on complex hydrides

    Science.gov (United States)

    Zidan, Ragaiy

    2016-04-26

    A battery and process of operating a battery system is provided using high hydrogen capacity complex hydrides in an organic non-aqueous solvent that allows the transport of hydride ions such as AlH.sub.4.sup.- and metal ions during respective discharging and charging steps.

  16. Ultra-sonic observation in niobium hydride precipitation

    International Nuclear Information System (INIS)

    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)

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

    Directory of Open Access Journals (Sweden)

    Thirugnasambandam G. Manivasagam

    2012-10-01

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

  18. Modular hydride beds for mobile applications

    Energy Technology Data Exchange (ETDEWEB)

    Malinowski, M.E.; Stewart, K.D.

    1997-08-01

    Design, construction, initial testing and simple thermal modeling of modular, metal hydride beds have been completed. Originally designed for supplying hydrogen to a fuel cell on a mobile vehicle, the complete bed design consists of 8 modules and is intended for use on the Palm Desert Vehicle (PDV) under development at the Schatz Energy Center, Humbolt State University. Each module contains approximately 2 kg of a commercially available, low temperature, hydride-forming metal alloy. Waste heat from the fuel cell in the form of heated water is used to desorb hydrogen from the alloy for supplying feed hydrogen to the fuel cell. In order to help determine the performance of such a modular bed system, six modules were constructed and tested. The design and construction of the modules is described in detail. Initial testing of the modules both individually and as a group showed that each module can store {approximately} 30 g of hydrogen (at 165 PSIA fill pressure, 17 C), could be filled with hydrogen in 6 minutes at a nominal, 75 standard liters/min (slm) fueling rate, and could supply hydrogen during desorption at rates of 25 slm, the maximum anticipated hydrogen fuel cell input requirement. Tests made of 5 modules as a group indicated that the behavior of the group run in parallel both in fueling and gas delivery could be directly predicted from the corresponding, single module characteristics by using an appropriate scaling factor. Simple thermal modeling of a module as an array of cylindrical, hydride-filled tubes was performed. The predictions of the model are in good agreement with experimental data.

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

    International Nuclear Information System (INIS)

    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) GdH2 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 GdH2 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 the

  20. Low-frequency excitations in zirconium hydrides

    International Nuclear Information System (INIS)

    The slow inelastic neutron scattering (INS) on ZrHx 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

  1. Tritium immobilization and packaging using metal hydrides

    International Nuclear Information System (INIS)

    Tritium recovered from CANDU heavy water reactors will have to be packaged and stored in a safe manner. Tritium will be recovered in the elemental form, T2. Metal tritides are effective compounds in which to immobilize the tritium as a stable non-reactive solid with a high tritium capacity. The technology necessary to prepare hydrides of suitable metals, such as titanium and zirconium, have been developed and the properties of the prepared materials evaluated. Conceptual designs of packages for containing metal tritides suitable for transportation and long-term storage have been made and initial testing started. (author)

  2. Metal hydrides for concentrating solar thermal power energy storage

    Science.gov (United States)

    Sheppard, D. A.; Paskevicius, M.; Humphries, T. D.; Felderhoff, M.; Capurso, G.; Bellosta von Colbe, J.; Dornheim, M.; Klassen, T.; Ward, P. A.; Teprovich, J. A.; Corgnale, C.; Zidan, R.; Grant, D. M.; Buckley, C. E.

    2016-04-01

    The development of alternative methods for thermal energy storage is important for improving the efficiency and decreasing the cost of concentrating solar thermal power. We focus on the underlying technology that allows metal hydrides to function as thermal energy storage (TES) systems and highlight the current state-of-the-art materials that can operate at temperatures as low as room temperature and as high as 1100 °C. The potential of metal hydrides for thermal storage is explored, while current knowledge gaps about hydride properties, such as hydride thermodynamics, intrinsic kinetics and cyclic stability, are identified. The engineering challenges associated with utilising metal hydrides for high-temperature TES are also addressed.

  3. Recent advances in metal hydrides for clean energy applications

    Energy Technology Data Exchange (ETDEWEB)

    Ronnebro, Ewa; Majzoub, Eric H.

    2013-06-01

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

  4. Helium trapping at erbium oxide precipitates in erbium hydride

    Energy Technology Data Exchange (ETDEWEB)

    Foiles, Stephen M. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Battaile, Corbett Chandler [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2016-02-01

    The formation of He bubbles in erbium tritides is a significant process in the aging of these materials. Due to the long-standing uncertainty about the initial nucleation process of these bubbles, there is interest in mechanisms that can lead to the localization of He in erbium hydrides. Previous work has been unable to identify nucleation sites in homogeneous erbium hydride. This work builds on the experimental observation that erbium hydrides have nano- scale erbium oxide precipitates due to the high thermodynamic stability of erbium oxide and the ubiquitous presence of oxygen during materials processing. Fundamental DFT calculations indicate that the He is energetically favored in the oxide relative to the bulk hydride. Activation energies for the motion of He in the oxide and at the oxide-hydride interface indicate that trapping is kinetically feasible. A simple kinetic Monte Carlo model is developed that demonstrates the degree of trapping of He as a function of temperature and oxide fraction.

  5. Results of NDE Technique Evaluation of Clad Hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Dennis C. Kunerth

    2014-09-01

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

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

    Science.gov (United States)

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

    2014-09-01

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

  7. Development of hydride absorber for fast reactor. Application of hafnium hydride to control rod of large fast reactor

    International Nuclear Information System (INIS)

    The application of hafnium hydride (Hf-hydride) to a control rod for a large fast reactor where the B4C control rod is originally employed is studied. Three types of Hf-hydride control rods are designed. The control rod worth and its change during the burnup are evaluated for different hydrogen-to-hafnium ratios and are compared with those of the original B4C control rod. The result indicates that the worths of the Hf-hydride and the 10B-enriched B4C control rods are approximately the same, and the lifetime of the Hf-hydride control rod is almost four times longer than that of the 10B-enriched B4C control rod. The core performances of the shutdown margin, sodium void reactivity, Doppler reactivity coefficient, and breeding ratio are analyzed. It is indicated that those for the Hf-hydride control rod are almost the same as those for the original B4C control rod. The behavior of neutrons moderated by the Hf-hydride control rod is analyzed. It is confirmed that the Hf-hydride control rod does not cause any thermal spike problems in the fast reactor core. (author)

  8. 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...

  9. Isotope exchange between gaseous hydrogen and uranium hydride powder

    International Nuclear Information System (INIS)

    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

  10. 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.

  11. PIE techniques for hydride reorientation test at NDC

    International Nuclear Information System (INIS)

    Dry storage of spent fuels in the interim storage facility is being planned in Japan. However, the gradual deterioration of the mechanical property of fuel cladding due to internal pressure and temperature during the storage term is known. Therefore, the integrity of stored fuel rods should be confirmed before the start of dry storage. For the last several years, NDC had a lot of experiences on the hydride reorientation test. The specimen preparation techniques on the hydride reorientation test and the mechanical testing techniques after the hydride reorientation are shown in this paper. (author)

  12. 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.

  13. The progress of nanocrystalline hydride electrode materials

    International Nuclear Information System (INIS)

    This paper reviews research at the Institute of Materials Science and Engineering, Poznan University of Technology, on the synthesis of nanocrystalline hydride electrode materials. Nanocrystalline materials have been synthesized by mechanical alloying (MA) followed by annealing. Examples of the materials include TiFe-, ZrV2-, LaNi5 and Mg2Ni-type phases. Details on the process used and the enhancement of properties due to the nanoscale structures are presented. The synthesized alloys were used as negative electrode materials for Ni-MH battery. The properties of hydrogen host materials can be modified substantially by alloying to obtain the desired storage characteristics. For example, it was found that the respective replacement of Fe in TiFe by Ni and/or by Cr, Co, Mo improved not only the discharge capacity but also the cycle life of these electrodes. The hydrogen storage properties of nanocrystalline ZrV2- and LaNi5-type powders prepared by mechanical alloying and annealing show no big difference with those of melt casting (polycrystalline) alloys. On the other hand, a partial substitution of Mg by Mn or Al in Mg2Ni alloy leads to an increase in discharge capacity, at room temperature. Furthermore, the effect of the nickel and graphite coating on the structure of some nanocrystalline alloys and the electrodes characteristics were investigated. In the case of Mg2Ni-type alloy mechanical coating with graphite effectively reduced the degradation rate of the studied electrode materials. The combination of a nanocrystalline TiFe-, ZrV2- and LaNi5-type hydride electrodes and a nickel positive electrode to form a Ni-MH battery, has been successful. (authors)

  14. Artificial exomuscle investigations for applications-metal hydride

    International Nuclear Information System (INIS)

    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)

  15. Out-of-pile accelerated hydriding of Zircaloy fasteners

    International Nuclear Information System (INIS)

    Mechanical joints between Zircaloy and nickel-bearing alloys, mainly the Zircaloy-4/Inconel-600 combination, were exposed to water at 4500F and 5200F to study hydriding of Zircaloy in contact with a dissimilar metal. Accelerated hydriding of the Zircaloy occurred at both temperatures. At 4500F the dissolved hydrogen level of the water was over ten times that at 5200F. At 5200F the initially high hydrogen ingress rate decreased rapidly as exposure time increased and was effectively shut off in about 25 days. Severely hydrided Zircaloy components successfully withstood thermal cycling and mechanical testing. Chromium plating of the nickel-bearing parts was found to be an effective and practical barrier in preventing nickel-alloy smearing and accelerated hydriding of Zircaloy

  16. Artificial exomuscle investigations for applications-metal hydride

    Energy Technology Data Exchange (ETDEWEB)

    Crevier, Marie-Charlotte; Richard, Martin; Rittenhouse, D Matheson; Roy, Pierre-Olivier; Bedard, Stephane [Victhom Human Bionics Inc., Saint-Augustin-de-Desmaures, QC (Canada)

    2007-03-01

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

  17. Electronic structure and optical properties of lightweight metal hydrides

    NARCIS (Netherlands)

    Setten, van M.J.; Popa, V.A.; Wijs, de G.A.; Brocks, G.

    2007-01-01

    We study the dielectric functions of the series of simple hydrides LiH, NaH, MgH2, and AlH3, and of the complex hydrides Li3AlH6, Na3AlH6, LiAlH4, NaAlH4, and Mg(AlH4)2, using first-principles density-functional theory and GW calculations. All compounds are large gap insulators with GW single-partic

  18. 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.

  19. Thin-film metal hydrides for solar energy applications

    OpenAIRE

    2012-01-01

    Thin-film metal hydrides may become important solar energy materials in the future. This thesis demonstrates interesting material properties of metal hydride films, relevant for applications as semiconducting materials for photovoltaic (PV) solar cells and for regulation of light using smart window technology. List of papers. Papers II-VI are removed from the thesis due to copyright restrictions. Paper I C. Platzer-Björkman, T. Mongstad, S. Zh. Karazhanov, J. P. Mæhlen, E. S. Marst...

  20. Method of selective reduction of polyhalosilanes with alkyltin hydrides

    Science.gov (United States)

    Sharp, Kenneth G.; D'Errico, John J.

    1989-01-01

    The invention relates to the selective and stepwise reduction of polyhalosilanes by reacting at room temperature or below with alkyltin hydrides without the use of free radical intermediates. Alkyltin hydrides selectively and stepwise reduce the Si--Br, Si--Cl, or Si--I bonds while leaving intact any Si--F bonds. When two or more different halogens are present on the polyhalosilane, the halogen with the highest atomic weight is preferentially reduced.

  1. Method of selective reduction of halodisilanes with alkyltin hydrides

    Science.gov (United States)

    D'Errico, John J.; Sharp, Kenneth G.

    1989-01-01

    The invention relates to the selective and sequential reduction of halodisilanes by reacting these compounds at room temperature or below with trialkyltin hydrides or dialkyltin dihydrides without the use of free radical intermediates. The alkyltin hydrides selectively and sequentially reduce the Si-Cl, Si-Br or Si-I bonds while leaving intact the Si-Si and Si-F bonds present.

  2. Groundwater seepage from the Ranger uranium mine tailings dam: radioisotopes of radium, thorium and actinium. Supervising Scientist report 106

    International Nuclear Information System (INIS)

    Monitoring of bores near the Ranger uranium mine tailings dam has revealed deterioration in water quality in several bores since 1983. In a group of bores to the north of the dam, increases have been observed of up to 500 times for sulphate concentrations and of up to 5 times for 226Ra concentrations. Results are presented here of measurements of members of the uranium, thorium and actinium decay series in borewater samples collected between 1985 and 1993. In particular, measurements of all four naturally-occurring radium isotopes have been used in an investigation of the mechanism of radium concentration changes. For the most seepage-affected bores the major findings of the study include: 228Ra/226Ra 223Ra /226Ra and 224Ra/228Ra ratios all increased over the course of the study; barium concentrations show high seasonal variability, being lower in November than May, but strontium concentrations show a steady increase with time. Calculations show that the groundwater is probably saturated with respect to barite but not with respect to celestite or anglesite; sulphide concentrations are low in comparison with sulphate, and are higher in November than in May; and 227Ac concentrations have increased with time, but do not account for the high 223Ra/226Ra ratios. It is concluded on the basis of these observations that increases in Ra isotope concentrations observed in a number of seepage-affected bores arise from increases in salinity leading to desorption of radium from adsorption sites in the vicinity of the bore rather by direct transport of radium from the tailings. Increased salinity is also causing the observed increases in 227Ac and strontium concentrations, while formation of a barite solid phase in the groundwater is causing the removal of some radium from solution. This is the cause of the increasing radium isotope ratios noted above

  3. Novel fuel cell stack with coupled metal hydride containers

    Science.gov (United States)

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

    2016-10-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-09-30

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Li, Ruiwen, E-mail: ruiwenli@163.com; Wang, Xiaolin

    2014-06-01

    To study the behavior of hydrogen corrosion at the surface of U, U–2.5 wt%Nb alloy and U–5.7 wt%Nb, a gas–solid reaction system with an in situ microscope was designed. The nucleation and growth of the hydride of the alloy were continuously observed and recorded by a computer. The different characteristics of the hydrides on U metal and U–2.5 wt%Nb showed that the later alloy is more susceptible to hydrogen corrosion than the former. The growth rate of hydride of U–2.5 wt%Nb, calculated by measuring the perimeter of the hydride spots recorded by the in situ microscope, exhibited a reaction temperature dependency in the range of 40–160 °C, for pressure of 0.8 × 10{sup 5} Pa. An Arrhenius plot for growth rate versus temperature yielded activation energy of 24.34 kJ/mol for the hydriding of U–2.5 wt%Nb alloy. The maximum hydriding rate was obtained at 125 °C, whose thermodynamics reason was discussed.

  6. Chemical Hydride Slurry for Hydrogen Production and Storage

    Energy Technology Data Exchange (ETDEWEB)

    McClaine, Andrew W

    2008-09-30

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

  7. Simultaneous Heat and Mass Transfer in DU Hydriding

    International Nuclear Information System (INIS)

    The sources of nuclear fusion reaction are deuterium (D) and tritium (T). Generally, D is fused into T, which generates helium atoms and neutrons. At this time, a tremendous amount of energy is generated. D + T → 4He + n (E = 17.6 MeV) Hydrogen is a gas, and cannot be stored in large amounts. In addition, it can be explosive. Therefore, one of the storing methods for hydrogen is metal hydride. In this research, several kinds of metal hydrides including U, Zr, ZrCo, ZrNi, and LaNi5 have been simulated through modeling work of hydrogen absorption, desorption, and pressure effect in a bed using DU. For the exact modeling of the hydriding process, it is necessary to calculate simultaneous heat and mass transfer because, in the hydriding process, not only is hydrogen gas transported by mass transport and chemisorption but heat transfer also occurs through absorption. Therefore, in this paper, we tried to calculate the simultaneous heat and mass transfer using numerical analysis methods. Simultaneous heat and mass transfer in DU hydriding is well fitted compared to the experimental data, and is more reasonable considering only one variable. The hydriding process changes the temperature and atomic ratio simultaneously, and thus it is necessary to consider in company with two transport phenomena. The numerical analysis method applied Euler's method; however, the Runge-Kutta method is a more widely used numerical solution of a differential equation. Therefore, when analyzing the hydriding process, Runge-Kutta or another method will henceforth be applied

  8. Reactions of NO with nitrogen hydrides x

    Science.gov (United States)

    Mebel, A. M.; Lin, M. C.

    In this review, we consider the reactions of NO ( x 1,2) with the nitrogen x hydrides NH, NH and NH . The reactions are relevant to the post-combustion, non-catalytic reduction of NO with NH in the thermal de-NO process and with x x HNCO in the rapid reduction of NO as well as to the thermal decomposition of x some high-energy materials, including ammonium dinitramide. The practical importance has motivated considerable theoretical interest in these reactions. We review numerous ab - initio molecular orbital studies of potential energy surfaces for NO NH and theoretical calculations of their kinetic parameters, such as x y thermal rate constants and branching ratios of various products. The most advanced theoretical calculations are carried out using the Gaussian-2 family of methods which provides the chemical accuracy (within 2 kcal mol ) for the energetics and molecular parameters of the reactants, products, intermediates and transition states. We present a detailed comparison of the theoretical results with available experimental data. We show that the reactions of NO with NH and NH x are very fast because they occur without a barrier and lead to the formation of multiple products which include radicals and stable molecules. The reactions of NO with NH , taking place by the H abstraction to form NH and HNO , are slow x x but still relevant to the NH de-NO system, because of their fast reverse processes x which have not yet been measured experimentally.

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

    Science.gov (United States)

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

    2016-07-01

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

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

    Directory of Open Access Journals (Sweden)

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

    2011-05-01

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

  11. Multidimensional simulations of hydrides during fuel rod lifecycle

    Science.gov (United States)

    Stafford, D. S.

    2015-11-01

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

  12. 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.

  13. The effect of stress state on zirconium hydride reorientation

    Science.gov (United States)

    Cinbiz, Mahmut Nedim

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

  14. High-Spin Cobalt Hydrides for Catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Holland, Patrick L. [Yale University

    2013-08-29

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

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

    Science.gov (United States)

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

    2016-01-19

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

  16. A new heat storage system using metal hydrides

    Science.gov (United States)

    Ono, S.; Kawamura, M.; Ishido, Y.; Akiba, E.; Higano, S.

    The development of a prototype chemical heat storage system, designed for the accumulation of fairly high temperature (300 - 400 C) waste heat, and called the Hydriding Heat Storage system is presented. Mg2Ni hydride is used as the high temperature heat storing medium, and LaNi5H6 is used as a reservoir for the hydrogen released from the heat storing medium. The system has been in development since 1976, and a 2000 kcal heat capacity prototype system is to be completed by 1982. Basic investigations, i.e., reaction kinetics of absorption and desorption, and heat transfer characteristics of the hydride and/or the metal powder packed bed, are described.

  17. Kinetic and structural aspects of tantalum hydride formation

    Directory of Open Access Journals (Sweden)

    R. DIMITRIJEVIC

    2003-09-01

    Full Text Available Tantalum hydrides of various composition were synthesized by equilibrating tantalum with hydrogen at six different temperatures from 573 to 823 K, under a constant hydrogen pressure of 1 bar. Both the exact Ta/H mole ratios and the kinetic parameters of hydriding were determined on the basis of the dependence of the H/Ta mole ratio on time. The influence of stoichiometry on the appearance of X-ray powder diffractograms at room temperature was studied. As a consequence of hydriding, for ratios H/Ta > 0.2, the original bcc Ta-lattice undergoes distortion, manifesting itself as both a shift and a splitting of the X-ray patterns in the X-ray diffractograms. For samples with H/Ta < 0.2, the appearance of some superstructure reflections at low Bragg angles was noted, which suggests a long range ordering of hydrogen with orthorhombic symmetry.

  18. Theoretical Estimate of Hydride Affinities of Aromatic Carbonyl Compounds

    Institute of Scientific and Technical Information of China (English)

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

    2003-01-01

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

  19. Photoelectron spectroscopy of boron aluminum hydride cluster anions

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Haopeng; Zhang, Xinxing; Ko, Yeon Jae; Gantefoer, Gerd; Bowen, Kit H., E-mail: kbowen@jhu.edu, E-mail: kiran@mcneese.edu [Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218 (United States); Li, Xiang [Center for Space Science and Technology, University of Maryland–Baltimore County, Baltimore, Maryland 21250 (United States); Kiran, Boggavarapu, E-mail: kbowen@jhu.edu, E-mail: kiran@mcneese.edu [Department of Chemistry and Physics, McNeese State University, Lake Charles, Louisiana 70609 (United States); Kandalam, Anil K. [Department of Physics, West Chester University, West Chester, Pennsylvania 19383 (United States)

    2014-04-28

    Boron aluminum hydride clusters are studied through a synergetic combination of anion photoelectron spectroscopy and density functional theory based calculations. Boron aluminum hydride cluster anions, B{sub x}Al{sub y}H{sub z}{sup −}, were generated in a pulsed arc cluster ionization source and identified by time-of-flight mass spectrometry. After mass selection, their photoelectron spectra were measured by a magnetic bottle-type electron energy analyzer. The resultant photoelectron spectra as well as calculations on a selected series of stoichiometries reveal significant geometrical changes upon substitution of aluminum atoms by boron atoms.

  20. Ab-initio study of transition metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-04-24

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

  1. 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

  2. Comparison of irradiation hardening and microstructure evolution in ion-irradiated delta and epsilon hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Oono, Naoko, E-mail: n-oono@eng.hokudai.ac.jp [Institute of Advanced Energy, Kyoto University, Gokasho, Uji, Kyoto 611-0011 (Japan); Kasada, Ryuta [Institute of Advanced Energy, Kyoto University, Gokasho, Uji, Kyoto 611-0011 (Japan); Higuchi, Toru; Sakamoto, Kan; Nakatsuka, Masafumi [Nippon Nuclear Fuel Development Co., Ltd., 2163 Naritacho Oarai, Higashi-Ibaraki, Ibaraki 311-1313 (Japan); Hasegawa, Akiko; Kondo, Sosuke; Iwata, Noriyuki Y.; Matsui, Hideki; Kimura, Akihiko [Institute of Advanced Energy, Kyoto University, Gokasho, Uji, Kyoto 611-0011 (Japan)

    2013-11-15

    A δ-Zr-hydride was irradiated with 6.4 MeV Fe{sup 3+} ions to clarify the relationship between hardening and microstructural changes of bulk Zr-hydrides under neutron irradiation. Irradiation hardening was measured by nanoindentation tests. Transmission electron microscope cross-sectional observations showed that the deformation mechanism of the δ-Zr-hydride was both slip and twinning. Dislocation loops were observed in the irradiated hydride matrix. These irradiation-induced defects make slip deformation difficult and consequently promote the twin deformation of δ-Zr-hydride. This work is a continuation of the previous our work (J. Nucl. Mater. 419 (2011) 366–370) focused upon ε-Zr-hydride and we discuss a comparison between the two Zr-hydrides.

  3. 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...

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

    Science.gov (United States)

    Congdon, James W.

    2009-03-17

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

  5. Structural deformation of metallic uranium surrounding hydride growth sites

    International Nuclear Information System (INIS)

    Highlights: • UH3 formation on uranium surfaces by a controlled uptake of hydrogen at 240 °C. • Large hydride growths (35–125 μm in diameter) form at the surface. • Confined hydride expansion during growth generates stress in the subsurface. • EBSD scans found micro-cracking and twins as forms of stress relief in the metal. - Abstract: Electron backscatter diffraction (EBSD) was utilised to probe the microstructure of uranium metal in the vicinity of surface corrosion pits, resulting from hydrogen exposure (5 × 104 Pa, at 240 °C). Microstructural analysis of the surface revealed a subtle increase of grain orientation variation for grains at the border of the hydride growths. Cross sectional analysis, at pit sites, revealed significant microstructure deformation in the form of crystal twinning and micro-cracking beneath the surface. These observations provide qualitative evidence that local stress intensities generated as a consequence of hydride growth and confinement, were sufficient to cause deformation within the parent metal

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

    International Nuclear Information System (INIS)

    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)

  7. Diffusion model of delayed hydride cracking in zirconium alloys

    NARCIS (Netherlands)

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

    2004-01-01

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

  8. Electrochromism of Mg-Ni hydride switchable mirrors

    Science.gov (United States)

    Isidorsson, Jan; Giebels, I. A. M. E.; Di Vece, M.; Griessen, Ronald

    2001-11-01

    Switchable mirrors have so far been made of rare-earth and rare-earth-magnesium based metal-hydrides. In this investigation we study Mg-Ni-hydrides, which have been shown by Richardson et al. to exhibit switchable properties similar to those of the rare-earth hydrides. Cyclic voltammetry on MgzNiHx samples with 0.8 less than z less than 3.7 shows that addition of one Mg atom per Mg2Ni gives the best ab/desorption kinetics for hydrogen. X- ray diffraction reveals a structural change as hydrogen is absorbed. The metal-insulator transition is confirmed with simultaneous resistivity measurements. A pressure- composition isotherm of Mg2NiHx is also determined electrochemically. Optical spectrometry during gas loading gives an optical band gap of 1.6 eV for Mg2NiH4. This gap increases with increasing Mg content in a way similar to that of the Mg-doped rare-earth hydrides.

  9. 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 stora

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-10-05

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

  11. Synthesis and enhanced hydrogen desorption kinetics of magnesium hydride using hydriding chemical vapor synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Jin-Ho [Icheon Branch, Korea Institute of Ceramic Engineering and Technology (KICET), Icheon-si, Gyeonggi-do (Korea, Republic of); Kim, Byung-Goan [Korea Energy Materials Co.Ltd., 409, Daegu Technopark, 1-11, Hosan-Dong, Dalse-Gu 704-230 (Korea, Republic of); Kang, Yong-Mook, E-mail: dake@kaist.ac.kr [Department of Chemistry, Dongguk University-Seoul, 100715 Seoul (Korea, Republic of)

    2012-07-15

    Highlights: Black-Right-Pointing-Pointer We synthesized pure MgH{sub 2} by a hydriding chemical vapor synthesis process in a hydrogen atmosphere. Black-Right-Pointing-Pointer The particle size HCVS-MgH{sub 2} was drastically reduced to the sub-micron or micrometer-scale. Black-Right-Pointing-Pointer HCVS-MgH{sub 2} showed different shapes (needle-like nanofibers and angulated plate) depending on the deposited position. Black-Right-Pointing-Pointer HCVS-MgH{sub 2} desorbed hydrogen up to about 7.2 wt% and 7.1 wt%. - Abstract: This paper describes the hydriding chemical vapor synthesis (HCVS) of the hydrogen storage alloy MgH{sub 2} in a hydrogen atmosphere and the product's hydrogenation properties. Mg powder was used as a starting material to produce submicron MgH{sub 2} and uniformly heated to a temperature of 600 Degree-Sign C for Mg vaporization. The effects of deposited positions in HCVS reactor on the morphology and the composition of the obtained products were examined by using X-ray diffraction (XRD), scanning electron microscopy (SEM), and Brunauer-Emmett-Teller (BET) analyses. It is clearly seen that after the HCVS process, the particle size of synthesized MgH{sub 2} was drastically reduced to the sub-micron or micrometer-scale and these showed different shapes (needle-like nanofibers and angulated plate) depending on the deposited position. The hydrogen desorption temperatures of HCVS-MgH{sub 2} were measured using a differential scanning calorimeter (DSC). It was found that after the HCVS process, the desorption temperature of HCVS-MgH{sub 2} decreased from 430 to 385 Degree-Sign C and, simultaneously, the smallest particle size and the highest specific surface area were obtained. These observations indicate that the minimum hydrogen desorption temperature of HCVS-MgH{sub 2} powder with needle-like form can be obtained, and that this temperature is dependent on the particle size and the specific surface area of the products. The thermogravimetric

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-02-01

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

  13. Effects of metastability on hydrogen sorption in fluorine substituted hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Pinatel, E.R.; Corno, M.; Ugliengo, P.; Baricco, M., E-mail: marcello.baricco@unito.it

    2014-12-05

    Highlights: • Fluorine substitution in simple metal hydrides has been modelled. • The stability of the MH{sub (1−x)}F{sub x} solid solutions has been discussed. • Conditions for reversibility of sorption reactions have been suggested. - Abstract: In this work ab initio calculations and Calphad modelling have been coupled to describe the effect of fluorine substitution on the thermodynamics of hydrogenation–dehydrogenation in simple hydrides (NaH, AlH{sub 3} and CaH{sub 2}). These example systems have been used to discuss the conditions required for the formation of a stable hydride–fluoride solid solution necessary to obtain a reversible hydrogenation reaction.

  14. X-ray photoemission spectroscopy study of zirconium hydride

    International Nuclear Information System (INIS)

    X-ray photoemission spectroscopy (XPS) measurements are reported for ZrH/sub 1.65/ and Zr metal. The valence-band measurements are compared with available band-theory density-of-states calculations for the metal and hydride. The hydride spectrum differs significantly from the metal spectrum. Most important, a strong peak associated with hydrogen s electrons appears approximately 7 eV below the Fermi level. XPS measurements of Zr 4p core levels show a binding-energy shift of 1 eV between Zr metal and ZrH/sub 1.65/. It is argued that this shift results from charge readjustment in the vicinity of the Zr site. With the addition of hydrogen, net charge must be transferred from the Zr site to the hydrogen site. A charge-density analysis based on simplified cluster calculations is presented

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

    International Nuclear Information System (INIS)

    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

  16. 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.

  17. Effect of thermo-mechanical cycling on zirconium hydride reorientation studied in situ with synchrotron X-ray diffraction

    Science.gov (United States)

    Colas, Kimberly B.; Motta, Arthur T.; Daymond, Mark R.; Almer, Jonathan D.

    2013-09-01

    The circumferential hydrides normally present in nuclear reactor fuel cladding after reactor exposure may dissolve during drying for dry storage and re-precipitate when cooled under load into a more radial orientation, which could embrittle the fuel cladding. It is necessary to study the rates and conditions under which hydride reorientation may happen in order to assess fuel integrity in dry storage. The objective of this work is to study the effect of applied stress and thermal cycling on the hydride morphology in cold-worked stress-relieved Zircaloy-4 by combining conventional metallography and in situ X-ray diffraction techniques. Metallography is used to study the evolution of hydride morphology after several thermo-mechanical cycles. In situ X-ray diffraction performed at the Advanced Photon Source synchrotron provides real-time information on the process of hydride dissolution and precipitation under stress during several thermal cycles. The detailed study of diffracted intensity, peak position and full-width at half-maximum provides information on precipitation kinetics, elastic strains and other characteristics of the hydride precipitation process. The results show that thermo-mechanical cycling significantly increases the radial hydride fraction as well as the hydride length and connectivity. The radial hydrides are observed to precipitate at a lower temperature than circumferential hydrides. Variations in the magnitude and range of hydride strains due to reorientation and cycling have also been observed. These results are discussed in light of existing models and experiments on hydride reorientation. The study of hydride elastic strains during precipitation shows marked differences between circumferential and radial hydrides, which can be used to investigate the reorientation process. Cycling under stress above the threshold stress for reorientation drastically increases both the reoriented hydride fraction and the hydride size. The reoriented hydride

  18. Inelastic neutron scattering from amorphous hydride of Zr2Pd

    International Nuclear Information System (INIS)

    Time-of-flight inelastic neutron scattering data was obtained on hydrided Zr2Pd metallic glass using the Crystal Analyzer Spectrometer at the Los Alamos pulsed spallation neutron source. Energy transfers from about 40 MeV to several hundred MeV were obtained with sufficiently good statistics and signal to noise ratio to show the second harmonic as well as the fundamental hydrogen optic mode

  19. Proximity breakdown of hydrides in superconducting niobium cavities

    OpenAIRE

    Romanenko, A.; Barkov, F.; Cooley, L. D.; Grassellino, A.

    2012-01-01

    Many modern and proposed future particle accelerators rely on superconducting radio frequency cavities made of bulk niobium as primary particle accelerating structures. Such cavities suffer from the anomalous field dependence of their quality factors Q0. High field degradation - so-called high field Q-slope - is yet unexplained even though an empirical cure is known. Here we propose a mechanism based on the presence of proximity-coupled niobium hydrides, which can explain this effect. Further...

  20. METHOD OF MAKING DELTA ZIRCONIUM HYDRIDE MONOLITHIC MODERATOR PIECES

    Science.gov (United States)

    Vetrano, J.B.

    1962-01-23

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

  1. Hydrogen storage materials and metal hydride-Ni batteries

    International Nuclear Information System (INIS)

    The hydrogen storage alloy is the key active material in metal hydride-Ni (MH-Ni) batteries. A brief review of hydrogen storage negative electrode materials including misch-nickel-based alloys, Laves phase alloys, magnesium-based alloys, vanadium-based solid solutions and nanotubes is presented. Current problems that need to be solved are mentioned. In addition, recent developments of MH/Ni-batteries with high power and energy are introduced

  2. 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.

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

    OpenAIRE

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

    2015-01-01

    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 obser...

  4. High Temperature Metal Hydrides as Heat Storage Materials for Solar and Related Applications

    Directory of Open Access Journals (Sweden)

    Borislav Bogdanović

    2009-01-01

    Full Text Available For the continuous production of electricity with solar heat power plants the storage of heat at a temperature level around 400 °C is essential. High temperature metal hydrides offer high heat storage capacities around this temperature. Based on Mg-compounds, these hydrides are in principle low-cost materials with excellent cycling stability. Relevant properties of these hydrides and their possible applications as heat storage materials are described.

  5. High Temperature Metal Hydrides as Heat Storage Materials for Solar and Related Applications

    OpenAIRE

    Borislav Bogdanović; Michael Felderhoff

    2009-01-01

    For the continuous production of electricity with solar heat power plants the storage of heat at a temperature level around 400 °C is essential. High temperature metal hydrides offer high heat storage capacities around this temperature. Based on Mg-compounds, these hydrides are in principle low-cost materials with excellent cycling stability. Relevant properties of these hydrides and their possible applications as heat storage materials are described.

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

    OpenAIRE

    Jun-qin Wang; Jian-feng Gao; Zhi-gang Wu; Guo-li Ou; Yu Wang

    2015-01-01

    The research on hydrogen generation and application has attracted widespread attention around the world. This paper is to demonstrate that sodium aluminum hydride can be synthesized under simple and mild reaction condition. Being activated through organics, aluminum powder reacts with hydrogen and sodium hydride to produce sodium aluminum hydride under atmospheric pressure. The properties and composition of the sample were characterized by FTIR, XRD, SEM, and so forth. The results showed that...

  7. Superconductivity of novel tin hydrides (SnnHm) under pressure

    Science.gov (United States)

    Mahdi Davari Esfahani, M.; Wang, Zhenhai; Oganov, Artem R.; Dong, Huafeng; Zhu, Qiang; Wang, Shengnan; Rakitin, Maksim S.; Zhou, Xiang-Feng

    2016-01-01

    With the motivation of discovering high-temperature superconductors, evolutionary algorithm USPEX is employed to search for all stable compounds in the Sn-H system. In addition to the traditional SnH4, new hydrides SnH8, SnH12 and SnH14 are found to be thermodynamically stable at high pressure. Dynamical stability and superconductivity of tin hydrides are systematically investigated. Im2-SnH8, C2/m-SnH12 and C2/m-SnH14 exhibit higher superconducting transition temperatures of 81, 93 and 97 K compared to the traditional compound SnH4 with Tc of 52 K at 200 GPa. An interesting bent H3–group in Im2-SnH8 and novel linear H in C2/m-SnH12 are observed. All the new tin hydrides remain metallic over their predicted range of stability. The intermediate-frequency wagging and bending vibrations have more contribution to electron-phonon coupling parameter than high-frequency stretching vibrations of H2 and H3. PMID:26964636

  8. Multidimensional Chemical Modeling. III. Abundance and excitation of diatomic hydrides

    CERN Document Server

    Bruderer, Simon; Stäuber, P; Doty, Steven D

    2010-01-01

    The Herschel Space Observatory opens the sky for observations in the far infrared at high spectral and spatial resolution. A particular class of molecules will be directly observable; light diatomic hydrides and their ions (CH, OH, SH, NH, CH+, OH+, SH+, NH+). These simple constituents are important both for the chemical evolution of the region and as tracers of high-energy radiation. If outflows of a forming star erode cavities in the envelope, protostellar far UV (FUV; 6 100 K) for water ice to evaporate. If the cavity shape allows FUV radiation to penetrate this hot-core region, the abundance of FUV destroyed species (e.g. water) is decreased. In particular, diatomic hydrides and their ions CH$+, OH+ and NH+ are enhanced by many orders of magnitude in the outflow walls due to the combination of high gas temperatures and rapid photodissociation of more saturated species. The enhancement of these diatomic hydrides is sufficient for a detection using the HIFI and PACS instruments onboard Herschel. The effect...

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

    Science.gov (United States)

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

    2015-01-01

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

  10. Performance study of a hydrogen powered metal hydride actuator

    Science.gov (United States)

    Mainul Hossain Bhuiya, Md; Kim, Kwang J.

    2016-04-01

    A thermally driven hydrogen powered actuator integrating metal hydride hydrogen storage reactor, which is compact, noiseless, and able to generate smooth actuation, is presented in this article. To test the plausibility of a thermally driven actuator, a conventional piston type actuator was integrated with LaNi5 based hydrogen storage system. Copper encapsulation followed by compaction of particles into pellets, were adopted to improve overall thermal conductivity of the reactor. The operation of the actuator was thoroughly investigated for an array of operating temperature ranges. Temperature swing of the hydride reactor triggering smooth and noiseless actuation over several operating temperature ranges were monitored for quantification of actuator efficiency. Overall, the actuator generated smooth and consistent strokes during repeated cycles of operation. The efficiency of the actuator was found to be as high as 13.36% for operating a temperature range of 20 °C-50 °C. Stress-strain characteristics, actuation hysteresis etc were studied experimentally. Comparison of stress-strain characteristics of the proposed actuator with traditional actuators, artificial muscles and so on was made. The study suggests that design modification and use of high pressure hydride may enhance the performance and broaden the application horizon of the proposed actuator in future.

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

    International Nuclear Information System (INIS)

    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)

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

    Directory of Open Access Journals (Sweden)

    Jun-qin Wang

    2015-01-01

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

  13. Reactivity patterns of transition metal hydrides and alkyls

    Energy Technology Data Exchange (ETDEWEB)

    Jones, W.D. II

    1979-05-01

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

  14. Reactivity patterns of transition metal hydrides and alkyls

    International Nuclear Information System (INIS)

    The complex PPN+ CpV(CO)3H- (Cp=eta5-C5H5 and PPN = (Ph3P)2) was prepared in 70% yield and its physical properties and chemical reactions investigated. PPN+ CpV(CO)3H- reacts with a wide range of organic halides. The organometallic products of these reactions are the vanadium halides PPN+[CpV(C)3X]- and in some cases the binuclear bridging hydride PPN+ [CpV(CO)3]2H-. The borohydride salt PPN+[CpV(CO)3BH4]- has also been prepared. The reaction between CpV(CO)3H- 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)3H-. Sodium amalgam reduction of CpRh(CO)2 or a mixture of CpRh(CO)2 and CpCo(CO)2 affords two new anions, PPN+ [Cp2Rh3(CO)4]- and PPN+[Cp2RhCo(CO)2]-. CpMo(CO)3H reacts with CpMo(CO)3R (R=CH3,C2H5, CH2C6H5) at 25 to 500C to produce aldehyde RCHO and the dimers [CpMo(CO)3]2 and [CpMo(CO)2]2. In general, CpV(CO)3H- appears to transfer a hydrogen atom to the metal radical anion formed in an electron transfer process, whereas CpMo(CO)3H transfers hydride in a 2-electron process to a vacant coordination site. The chemical consequences are that CpV(CO)3H- generally reacts with metal alkyls to give alkanes via intermediate alkyl hydride species whereas CpMo(CO)3H reacts with metal alkyls to produce aldehyde, via an intermediate acyl hydride species

  15. Determination of fracture strength of δ-zirconium hydrides embedded in zirconium matrix at high temperatures

    Science.gov (United States)

    Kubo, T.; Kobayashi, Y.; Uchikoshi, H.

    2013-04-01

    The fracture strength of δ-zirconium hydrides embedded in a zirconium matrix was determined at temperatures between 25 °C and 250 °C by ring tensile tests using Zircaloy-2 tubes. Essentially all of the present hydrides in the tubes were re-oriented in the radial direction by a temperature cycling treatment and then tensile stress was applied perpendicular to the hydrides to ensure that brittle fracture would occur at the hydrides. The hydrides failed in a brittle manner below 100 °C where-as the zirconium matrix itself underwent ductile fracture without hydride cracking at temperatures above 200 °C under plane stress condition. Brittle fracture of the hydrides continued to occur at temperatures up to 250 °C under plane strain condition, suggesting that the upper limit temperature for hydride fracture, Tupper, was raised by the triaxial stress state under the plane strain condition. The apparent fracture strength of the hydrides, σhydridef, was determined at temperatures below Tupper from the measured fracture strength of the tubes, making a correction for the compressive transformation stress in the hydrides. σhydridef was about 710 MPa at temperatures between 25 °C and 250 °C at both plane stress and plane strain conditions. The temperature dependency was very small in this temperature range. Tupper was almost equivalent to the cross-over temperature between σhydridef and the ultimate tensile strength (UTS), which suggests that, at temperatures above Tupper, the zirconium matrix would undergo ductile fracture before the stress in the hydride is raised above σhydridef, since UTS is smaller than σhydridef.

  16. Experiments on hadronic-atom x-ray intensities of hydrides and deuterides

    Energy Technology Data Exchange (ETDEWEB)

    Wiegand, C.E.; Lum, G.K.; Godfrey, G.L.

    1977-04-01

    Kaonic-atom x-ray intensities of elements Z = 3, 6, 8, 11, and 20 were significantly reduced when the elements were in hydride form. The ratios I (ZH/sub m/)/I (Z) have a noticeable Z dependence. Deuterides of C and O showed slightly less x-ray emission than their hydride counterparts.

  17. Study on the Use of Hydride Fuel in High-Performance Light Water Reactor Concept

    Directory of Open Access Journals (Sweden)

    Haileyesus Tsige-Tamirat

    2015-01-01

    Full Text Available Hydride fuels have features which could make their use attractive in future advanced power reactors. The potential benefit of use of hydride fuel in HPLWR without introducing significant modification in the current core design concept of the high-performance light water reactor (HPLWR has been evaluated. Neutronics and thermal hydraulic analyses were performed for a single assembly model of HPLWR with oxide and hydride fuels. The hydride assembly shows higher moderation with softer neutron spectrum and slightly more uniform axial power distribution. It achieves a cycle length of 18 months with sufficient excess reactivity. At Beginning of Cycle the fuel temperature coefficient of the hydride assembly is higher whereas the moderator and void coefficients are lower. The thermal hydraulic results show that the achievable fuel temperature in the hydride assembly is well below the design limits. The potential benefits of the use of hydride fuel in the current design of the HPLWR with the achieved improvements in the core neutronics characteristics are not sufficient to justify the replacement of the oxide fuel. Therefore for a final evaluation of the use of hydride fuels in HPLWR concepts additional studies which include modification of subassembly and core layout designs are required.

  18. Thermal and mechanical properties of zirconium hydrides with various hafnium contents

    International Nuclear Information System (INIS)

    Zirconium (Zr) hydride is currently expected as a neutron shield material for fast reactors. In order to evaluate safety and economic efficiency of the nuclear reactor, the thermal and mechanical properties of the hydride should be understood. In addition, since chemical properties of Zr and hafnium (Hf) are quite similar, Zr contains a few percent Hf generally. Therefore, it is very important to evaluate the effect of Hf content on the properties of Zr hydride. In the present study, fine bulk samples of δ-phase Zr hydrides with various Hf contents were prepared and their thermal and mechanical properties were investigated. We examined the phase states and the microstructure of the hydrides by means of X-ray diffraction and SEM/EDX analyses. In the temperature range from room temperature to 673 K, the heat capacity and the thermal diffusivity of the hydrides were measured and the thermal conductivity was evaluated. The Vickers hardness and the sound velocity of the hydrides were measured at room temperature, and the elastic modulus was calculated from the measured sound velocity. The effects of temperature and Hf content on the properties of Zr hydrides were studied. (author)

  19. Hydride precipitation and its influence on mechanical properties of notched and unnotched Zircaloy-4 plates

    International Nuclear Information System (INIS)

    The hydride formation and its influence on the mechanical performance of hydrided Zircaloy-4 plates containing different hydrogen contents were studied at room temperature. For the unnotched plate samples with the hydrogen contents ranging from 25 to 850 wt. ppm, the hydrides exerted an insignificant effect on the tensile strength, while the ductility was severely degraded with increasing hydrogen content. The fracture mode and degree of embrittlement were strongly related to the hydrogen content. When the hydrogen content reached a level of 850 wt. ppm, the plate exhibited negligible ductility, resulting in almost completely brittle behavior. For the hydrided notched plate, the tensile stress concentration associated with the notch tip facilitated the hydride accumulation at the region near the notch tip and the premature crack propagation through the hydride fracture during hydriding. The final brittle through-thickness failure for this notched sample was mainly attributed to the formation of a continuous hydride network on the thickness section and the obtained very high hydrogen concentration (estimated to be 1965 wt. ppm)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1995-09-01

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

  1. Uranium-zirconium hydride TRIGA-LEU fuel

    International Nuclear Information System (INIS)

    The development and testing of TRIGA-LEU fuel with up to 45 wt-% U is described. Topics that are discussed include properties of hydride fuels, the prompt negative temperature coefficient, pulse heating tests, fission product retention, and the limiting design basis parameter and values. General specifications for Er-U-ZrH TRIGA-LEU fuel with 8.5 to 45 wt-% U and an outline of the inspections during manufacture of the fuel are also included. (author). 8 figs, 1 tab

  2. Hydride Ions, HCO+ and Ionizing Irradiation in Star Forming Region

    Science.gov (United States)

    Benz, Arnold O.; Bruderer, Simon; van Dishoeck, Ewine

    2016-06-01

    Hydrides are fundamental precursor molecules in cosmic chemistry and many hydride ions have become observable in high quality for the first time thanks to the Herschel Space Observatory. Ionized hydrides, such as CH+ and OH+ and also HCO+ affect the chemistry of molecules such as water. They also provide complementary information on irradiation by far UV (FUV) or X-rays and gas temperature.We explore hydrides of the most abundant heavier elements in an observational survey covering star forming regions with different mass and evolutionary state. Twelve YSOs were observed with HIFI on Herschel in 6 spectral settings providing fully velocity-resolved line profiles. The YSOs include objects of low (Class 0 and I), intermediate, and high mass, with luminosities ranging from 4 Ls to 2 105 Ls.The targeted lines of CH+, OH+, H2O+, and C+ are detected mostly in blue-shifted absorption. H3O+ and SH+ are detected in emission and only toward some high-mass objects. For the low-mass YSOs the column density ratios of CH+/OH+ can be reproduced by simple chemical models implying an FUV flux of 2 – 400 times the ISRF at the location of the molecules. In two high-mass objects, the UV flux is 20 – 200 times the ISRF derived from absorption lines, and 300 – 600 ISRF using emission lines. Upper limits for the X-ray luminosity can be derived from H3O+ observations for some low-mass objects.If the FUV flux required for low-mass objects originates at the central protostar, a substantial FUV luminosity, up to 1.5 Ls, is required. For high-mass regions, the FUV flux required to produce the observed molecular ratios is smaller than the unattenuated flux expected from the central object(s) at the Herschel beam radius. This is consistent with an FUV flux reduced by circumstellar extinction or by bloating of the protostar.The ion molecules are proposed to form in FUV irradiated cavity walls that are shocked by the disk wind. The shock region is turbulent, broadening the lines to some 1

  3. Research in Nickel/Metal Hydride Batteries 2016

    Directory of Open Access Journals (Sweden)

    Kwo-Hsiung Young

    2016-10-01

    Full Text Available Nineteen papers focusing on recent research investigations in the field of nickel/metal hydride (Ni/MH batteries have been selected for this Special Issue of Batteries. These papers summarize the joint efforts in Ni/MH battery research from BASF, Wayne State University, the National Institute of Standards and Technology, Michigan State University, and FDK during 2015–2016 through reviews of basic operational concepts, previous academic publications, issued US Patent and filed Japan Patent Applications, descriptions of current research results in advanced components and cell constructions, and projections of future works.

  4. The calculated rovibronic spectrum of scandium hydride, ScH

    CERN Document Server

    Lodi, Lorenzo; Tennyson\\, Jonathan

    2015-01-01

    The electronic structure of six low-lying electronic states of scandium hydride, $X\\,{}^{1}\\Sigma^+$, $a\\,{}^{3}\\Delta$, $b\\,{}^{3}\\Pi$, $A\\,{}^{1}\\Delta$ $c\\,{}^{3}\\Sigma^+$, and $B\\,{}^{1}\\Pi$, is studied using multi-reference configuration interaction as a function of bond length. Diagonal and off-diagonal dipole moment, spin-orbit coupling and electronic angular momentum curves are also computed. The results are benchmarked against experimental measurements and calculations on atomic scandium. The resulting curves are used to compute a line list of molecular ro-vibronic transitions for $^{45}$ScH.

  5. Alkyl and Hydride-Olefin Complexes of Niobocene

    NARCIS (Netherlands)

    Klazinga, A.H.; Teuben, J.H.

    1980-01-01

    Reactions of Cp2NbCl2 with RMgCl (R = n-C3H7, i-C3H7, n-C4H9, s-C4H9 and n-C5H11) give niobocene hydride olefin complexes Cp2Nb(H)L (L = C3H6, C4H8 and C5H10). The last step of the reaction probably proceeds via a stereospecific β-H elimination from the monoalkyl species Cp2NbR. Decomposition of n-a

  6. Electrochemical process and production of novel complex hydrides

    Science.gov (United States)

    Zidan, Ragaiy

    2013-06-25

    A process of using an electrochemical cell to generate aluminum hydride (AlH.sub.3) is provided. The electrolytic cell uses a polar solvent to solubilize NaAlH.sub.4. The resulting electrochemical process results in the formation of AlH.sub.3. The AlH.sub.3 can be recovered and used as a source of hydrogen for the automotive industry. The resulting spent aluminum can be regenerated into NaAlH.sub.4 as part of a closed loop process of AlH.sub.3 generation.

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

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

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

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

    Institute of Scientific and Technical Information of China (English)

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

    2006-01-01

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

  9. 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

    2015-04-01

    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.

  10. Hydrogenation reaction characteristics and properties of its hydrides for magnetic regenerative material HoCu2

    Institute of Scientific and Technical Information of China (English)

    金滔; 吴梦茜; 黄迦乐; 汤珂; 陈立新

    2016-01-01

    The hydrogenation reaction characteristics and the properties of its hydrides for the magnetic regenerative material HoCu2 (CeCu2-type) of a cryocooler were investigated. The XRD testing reveals that the hydrides of HoCu2 were a mixture of Cu, unknown hydride I, and unknown hydride II. Based on the PCT (pressure−concentration−temperature) curves under different reaction temperatures, the relationships among reaction temperature, equilibrium pressure, and maximum hydrogen absorption capacity were analyzed and discussed. The enthalpy changeΔH and entropy changeΔS as a result of the whole hydrogenation process were also calculated from the PCT curves. The magnetization and volumetric specific heat capacity of the hydride were also measured by SQUID magnetometer and PPMS, respectively.

  11. Mobility and chemical bond of hydrogen in titanium and palladium hydrides

    International Nuclear Information System (INIS)

    The probabilities for π- meson capture by hydrogen are measured at 25, 155 and 200 deg C in TiHsub(1.65) hydride and at 25, -120 and -196 deg C in PdHsub(0.67) hydride. An analysis of the results obtained shows that within the accuracy of the measurements (approximately 10%) a sharp (up to 1012) change in the mobility of hydrogen in the hydrides induced by temperature changes within the ranges indicated does not noticeably affect the probabilities for π- meson capture by bound hydrogen, i.e. does not lead to appreciable changes in the Me-H bond. A comparison of the capture probabilities for palladium hydride and hydrides of neighboring transition metals shows that there are no pronounced anomalies in the Pd-H bond

  12. Formation of alloys in Ti-V system in hydride cycle and synthesis of their hydrides in self-propagating high-temperature synthesis regime

    Energy Technology Data Exchange (ETDEWEB)

    Aleksanyan, A.G., E-mail: a.g.aleks_yan@mail.ru [A.B. Nalbandyan Institute of Chemical Physics of Armenian NAS, 5/2 P.Sevak Str., Yerevan 0014 (Armenia); Dolukhanyan, S.K. [A.B. Nalbandyan Institute of Chemical Physics of Armenian NAS, 5/2 P.Sevak Str., Yerevan 0014 (Armenia); Shekhtman, V.Sh. [Institute of Solid State Physics, RAS, Chernogolovka, Moscow District 142432 (Russian Federation); Huot, J., E-mail: jacques_huot@uqtr.ca [Institut de recherche sur l' hydrogene, Universite du Quebec a Trois-Rivieres (Canada); Ter-Galstyan, O.P.; Mnatsakanyan, N.L. [A.B. Nalbandyan Institute of Chemical Physics of Armenian NAS, 5/2 P.Sevak Str., Yerevan 0014 (Armenia)

    2011-09-15

    Research highlights: > We synthesize Ti-V alloys by new 'hydride cycle' method. Structural characteristics of formed alloys we investigate by X-ray diffraction. > We show that the alloys contain mainly BCC crystal structure. > We investigate the interaction of the synthesized alloys with hydrogen in combustion regime. > We study the properties of hydrides by X-ray, DTA and DSC analyses. - Abstract: In the present work, the possibility of formation of titanium and vanadium based alloys of BCC structure using hydride cycle was investigated. The mechanism of formation of alloys in Ti-V system from the powders of hydrides TiH{sub 2} and VH{sub 0.9} (or of V) by compaction followed by dehydrogenation was studied. Then, the interaction of the synthesized alloys with hydrogen in combustion regime (self-propagating high-temperature synthesis, SHS) resulting in hydrides of these alloys was investigated. DTA and DSC analyses of some alloys and their hydrides were performed and their thermal characteristics were measured.

  13. Separation of covalent hydrides by gas-solid chromatography

    International Nuclear Information System (INIS)

    A fully automated method was developed for separating the hydrides of elements of the IVth to VIIIth main subgroup of the periodic system and of Kr and Xe on the basis of their volatility using gas chromatography. The automated instrument allowing to carry out reduction, separation of the gaseous phase, the loading of a PORAPAK-packed column, the chromatographic separation and sampling was controlled by a HP 2116B computer. The elution time, peak area and the number of theoretical column plates were computed from chromatograms. The capture probably proceeded by a type of nonpolar nonspecific sorption (ΔH/Tsub(b) = 19.2 cal/mol.deg). The height of the theoretical plate was 0.05 to 0.1 cm. The technique may be used as a routine radiochemical method for group separations and for the separation of radioactive hydrides contained in the solution of targets irradiated with neutrons or charged particles in the preparation of radioactive sources of short-lived radionuclides, or in destructive activation analysis. (M.K.)

  14. Reactions of ruthenium hydrides with ethyl-vinyl sulfide.

    Science.gov (United States)

    Dahcheh, Fatme; Stephan, Douglas W

    2014-03-01

    The Ru-hydride precursors (Im(OMe)2)(PPh3)2RuHCl () and (Me2Im(OMe)2)(PPh3)2RuHCl () reacted with ethyl-vinyl-sulfide to give ((MeOCH2CH2)C3H2N2(CH2CH(OMe))RuCl(PPh3)2 () and ((MeOCH2CH2)C3Me2N2(CH2CH(OMe))RuCl(PPh3)2 (), respectively. Dissolution of () in C6D6 prompts formation of ((MeOCH2CH2)C5H6N2(CHCH)RuCl(PPh3)2 (). The analogous reactions of the bis-carbene Ru-hydride precursors (Im(OMe)2)(IMes)(PPh3)RuHCl (), (Im(OMe)2)(SIMes)(PPh3)RuHCl () and (Im(OMe)2)(IMes-Cl2)(PPh3)RuHCl () gave ((MeOCH2CH2)C3H2N2(CHCH)RuCl(PPh3)(NHC) (NHC = IMes (), SIMes (), IMes-Cl2 (), respectively. The formation of compounds () and () is thought to go through an initial insertion of the vinyl-fragment into the Ru-H prompting subsequent C-H activation and loss of diethyl sulfide. This yields () and (), while subsequent loss of methanol yields () and (-). PMID:24441082

  15. Electronic structure of the palladium hydride studied by compton scattering

    CERN Document Server

    Mizusaki, S; Yamaguchi, M; Hiraoka, N; Itou, M; Sakurai, Y

    2003-01-01

    The hydrogen-induced changes in the electronic structure of Pd have been investigated by Compton scattering experiments associated with theoretical calculations. Compton profiles (CPs) of single crystal of Pd and beta phase hydride PdH sub x (x=0.62-0.74) have been measured along the [100], [110] and [111] directions with a momentum resolution of 0.14-0.17 atomic units using 115 keV x-rays. The theoretical Compton profiles have been calculated from the wavefunctions obtained utilizing the full potential linearized augmented plane wave method within the local density approximation for Pd and stoichiometric PdH. The experimental and the theoretical results agreed well with respect to the difference in the CPs between PdH sub x and Pd, and the anisotropy in the CPs of Pd or PdH sub x. This study provides lines of evidence that upon hydride formation the lowest valance band of Pd is largely modified due to hybridization with H 1s-orbitals and the Fermi energy is raised into the sp-band. (author)

  16. Gallium Nitride Nanowires Grown by Hydride Vapor Phase Epitaxy

    Institute of Scientific and Technical Information of China (English)

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

    2011-01-01

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

  17. Thermodynamic Calculation on the Formation of Titanium Hydride

    Institute of Scientific and Technical Information of China (English)

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

    2008-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1996-12-31

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

  19. Method of generating hydrogen-storing hydride complexes

    Science.gov (United States)

    Srinivasan, Sesha S; Niemann, Michael U; Goswami, D. Yogi; Stefanakos, Elias K

    2013-05-14

    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.

  20. Superconductive "sodalite"-like clathrate calcium hydride at high pressures

    CERN Document Server

    Wang, Hui; Tanaka, Kaori; Iitaka, Toshiaki; Ma, Yanming

    2012-01-01

    Hydrogen-rich compounds hold promise as high-temperature superconductors under high pressures. Recent theoretical hydride structures on achieving high-pressure superconductivity are composed mainly of H2 fragments. Through a systematic investigation of Ca hydrides with different hydrogen contents using particle-swam optimization structural search, we show that in the stoichiometry CaH6 a body-centred cubic structure with hydrogen that forms unusual "sodalite" cages containing enclathrated Ca stabilizes above pressure 150 GPa. The stability of this structure is derived from the acceptance by two H2 of electrons donated by Ca forming a "H4" unit as the building block in the construction of the 3-dimensional sodalite cage. This unique structure has a partial occupation of the degenerated orbitals at the zone centre. The resultant dynamic Jahn-Teller effect helps to enhance electron-phonon coupling and leads to superconductivity of CaH6. A superconducting critical temperature (Tc) of 220-235 K at 150 GPa obtained...

  1. A quantitative phase field model for hydride precipitation in zirconium alloys: Part I. Development of quantitative free energy functional

    International Nuclear Information System (INIS)

    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

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

    Science.gov (United States)

    Maity, Ayan; Teets, Thomas S

    2016-08-10

    This Review highlights stoichiometric reactions and elementary steps of catalytic reactions involving cooperative participation of transition-metal hydrides and main group Lewis acids. Included are reactions where the transition-metal hydride acts as a reactant as well as transformations that form the metal hydride as a product. This Review is divided by reaction type, illustrating the diverse roles that Lewis acids can play in mediating transformations involving transition-metal hydrides as either reactants or products. We begin with a discussion of reactions where metal hydrides form direct adducts with Lewis acids, elaborating the structure and dynamics of the products of these reactions. The bulk of this Review focuses on reactions where the transition metal and Lewis acid act in cooperation, and includes sections on carbonyl reduction, H2 activation, and hydride elimination reactions, all of which can be promoted by Lewis acids. Also included is a section on Lewis acid-base secondary coordination sphere interactions, which can influence the reactivity of hydrides. Work from the past 50 years is included, but the majority of this Review focuses on research from the past decade, with the intent of showcasing the rapid emergence of this field and the potential for further development into the future. PMID:27164024

  3. Generalized computational model for high-pressure metal hydrides with variable thermal properties

    DEFF Research Database (Denmark)

    Mazzucco, Andrea; Rokni, Masoud

    2015-01-01

    This study considers a detailed 1D fueling model applied to a metal hydride system, with Ti1.1CrMn as the absorbing alloy, to predict the weight fraction of the absorbed hydrogen and the solid bed temperature. Dependencies of thermal conductivity and specific heat capacity upon pressure...... and hydrogen content, respectively, are accounted for by interpolating experimental data. The effect of variable parameters on the critical metal hydride thickness is investigated and compared to results obtained from a constant-parameter analysis. Finally, the discrepancy in the metal hydride thickness value...

  4. Rapid Microwave Synthesis, Characterization and Reactivity of Lithium Nitride Hydride, Li4NH

    OpenAIRE

    Nuria Tapia-Ruiz; Natalie Sorbie; Nicolas Vaché; Hoang, Tuan K. A.; Gregory, Duncan H.

    2013-01-01

    Lithium nitride hydride, Li4NH, was synthesised from lithium nitride and lithium hydride over minute timescales, using microwave synthesis methods in the solid state for the first time. The structure of the microwave-synthesised powders was confirmed by powder X-ray diffraction [tetragonal space group I41/a; a = 4.8864(1) Å, c = 9.9183(2) Å] and the nitride hydride reacts with moist air under ambient conditions to produce lithium hydroxide and subsequently lithium carbonate. Li4NH undergoes n...

  5. Solid hydrides as hydrogen storage reservoirs; Hidruros solidos como acumuladores de hidrogeno

    Energy Technology Data Exchange (ETDEWEB)

    Fernandez, A.; Sanchez, C.; Friedrichs, O.; Ares, J. R.; Leardini, F.; Bodega, J.; Fernandez, J. F.

    2010-07-01

    Metal hydrides as hydrogen storage materials are briefly reviewed in this paper. Fundamental properties of metal-hydrogen (gas) system such as Pressure-Composition-Temperature (P-C-T) characteristics are discussed on the light of the metal-hydride thermodynamics. Attention is specially paid to light metal hydrides which might have application in the car and transport sector. The pros and cons of MgH{sub 2} as a light material are outlined. Researches in course oriented to improve the behaviour of MgH{sub 2} are presented. Finally, other very promising alternative materials such as Al compounds (alanates) or borohydrides as light hydrogen accumulators are also considered. (Author)

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

    Institute of Scientific and Technical Information of China (English)

    YANG; Donghui; HE; Deping; YANG; Shangrun

    2004-01-01

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

  7. Proton beam production by a laser ion source with hydride target

    Energy Technology Data Exchange (ETDEWEB)

    Okamura, M., E-mail: okamura@bnl.gov [Collider-Accelerator Department, Brookhaven National Laboratory, Upton, New York 11973 (United States); Nishina Center for Accelerator-Based Science, RIKEN, Saitama (Japan); Stifler, C. [Engineering Physics Systems Department, Providence College, Providence, Rhode Island 02918 (United States); Palm, K. [Department of Physics, Cornell University, Ithaca, New York 14853 (United States); Steski, D.; Kanesue, T. [Collider-Accelerator Department, Brookhaven National Laboratory, Upton, New York 11973 (United States); Ikeda, S. [Nishina Center for Accelerator-Based Science, RIKEN, Saitama (Japan); Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Kanagawa (Japan); Kumaki, M. [Nishina Center for Accelerator-Based Science, RIKEN, Saitama (Japan); Research Institute for Science and Engineering, Waseda University, Tokyo (Japan)

    2016-02-15

    We studied proton beam production from a laser ion source using hydrogen rich target materials. In general, gas based species are not suitable for laser ion sources since formation of a dense laser target is difficult. In order to achieve reliable operation, we tested hydride targets using a sub nanosecond Q-switched Nd-YAG laser, which may help suppress target material consumption. We detected enough yields of protons from a titanium hydride target without degradation of beam current during the experiment. The combination of a sub nanosecond laser and compressed hydride target may provide stable proton beam.

  8. Analytical control of production of As, P, Si, B hydrides and the mixtures on their basis

    International Nuclear Information System (INIS)

    Highly sensitive and selective detectors which are in the basis of some analytical devices, such as chromatograph Tzvet 500G attachment POU-80, gigrometer Enisej gas analyzer Platon that permit to control the production of As, P, Si, B hydrides, are tested. The techniques of tetermination of constant gases, general carbon, moisture in the mixtures based on As, P, Si, B hydrides with diluting gases (H2, He, Ar) as well as hydrides in them and in the air of working premises, are suggested

  9. Metal hydride hydrogen compression: recent advances and future prospects

    Science.gov (United States)

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

    2016-04-01

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

  10. Niche applications of metal hydrides and related thermal management issues

    Energy Technology Data Exchange (ETDEWEB)

    Lototskyy, M., E-mail: mlototskyy@uwc.ac.za [HySA Systems Competence Centre, South African Institute for Advanced Materials Chemistry, Faculty of Natural Sciences, University of the Western Cape, Private Bag X17, Bellville 7535 (South Africa); Satya Sekhar, B. [HySA Systems Competence Centre, South African Institute for Advanced Materials Chemistry, Faculty of Natural Sciences, University of the Western Cape, Private Bag X17, Bellville 7535 (South Africa); Muthukumar, P. [Mechanical Department, Indian Institute of Technology Guwahati, Guwahati 781039 (India); Linkov, V.; Pollet, B.G. [HySA Systems Competence Centre, South African Institute for Advanced Materials Chemistry, Faculty of Natural Sciences, University of the Western Cape, Private Bag X17, Bellville 7535 (South Africa)

    2015-10-05

    Highlights: • MH H{sub 2} storage, compression & heat management: developments/thermal management. • Thermodynamic criteria for proper selection of MH for different gas phase applications. • Factors influencing on H{sub 2} charge/discharge dynamic performance and energy efficiency. • The improvement of MH heat transfer characteristics is crucial. • Ways of improvement of heat transfer in the MH systems. - Abstract: This short review highlights and discusses the recent developments and thermal management issues related to metal hydride (MH) systems for hydrogen storage, hydrogen compression and heat management (refrigeration, pump and upgrade, etc.). Special attention is paid to aligning the system features with the requirements of the specific application. The considered system features include the MH material, the MH bed on the basis of its corresponding MH container, as well as the layout of the integrated system.

  11. Crystal structure of the superconducting phase of sulfur hydride

    Science.gov (United States)

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

    2016-09-01

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

  12. Pressure-induced transformations of molecular boron hydride

    CERN Document Server

    Nakano, S; Gregoryanz, E A; Goncharov, A F; Mao Ho Kwang

    2002-01-01

    Decaborane, a molecular boron hydride, was compressed to 131 GPa at room temperature to explore possible non-molecular phases in this system and their physical properties. Decaborane changed its colour from transparent yellow to orange/red above 50 GPa and then to black above 100 GPa, suggesting some transformations. Raman scattering and infrared (IR) absorption spectroscopy reveal significant structural changes. Above 100 GPa, B-B skeletal, B-H and B-H-B Raman/IR peaks gradually disappeared, which implies a transformation into a non-molecular phase in which conventional borane-type bonding is lost. The optical band gap of the material at 100 GPa was estimated to be about 1.0 eV.

  13. Niche applications of metal hydrides and related thermal management issues

    International Nuclear Information System (INIS)

    Highlights: • MH H2 storage, compression & heat management: developments/thermal management. • Thermodynamic criteria for proper selection of MH for different gas phase applications. • Factors influencing on H2 charge/discharge dynamic performance and energy efficiency. • The improvement of MH heat transfer characteristics is crucial. • Ways of improvement of heat transfer in the MH systems. - Abstract: This short review highlights and discusses the recent developments and thermal management issues related to metal hydride (MH) systems for hydrogen storage, hydrogen compression and heat management (refrigeration, pump and upgrade, etc.). Special attention is paid to aligning the system features with the requirements of the specific application. The considered system features include the MH material, the MH bed on the basis of its corresponding MH container, as well as the layout of the integrated system

  14. Final report for the DOE Metal Hydride Center of Excellence.

    Energy Technology Data Exchange (ETDEWEB)

    Keller, Jay O.; Klebanoff, Leonard E.

    2012-01-01

    This report summarizes the R&D activities within the U.S. Department of Energy Metal Hydride Center of Excellence (MHCoE) from March 2005 to June 2010. The purpose of the MHCoE has been to conduct highly collaborative and multi-disciplinary applied R&D to develop new reversible hydrogen storage materials that meet or exceed DOE 2010 and 2015 system goals for hydrogen storage materials. The MHCoE combines three broad areas: mechanisms and modeling (which provide a theoretically driven basis for pursuing new materials), materials development (in which new materials are synthesized and characterized) and system design and engineering (which allow these new materials to be realized as practical automotive hydrogen storage systems). This Final Report summarizes the organization and execution of the 5-year research program to develop practical hydrogen storage materials for light duty vehicles. Major results from the MHCoE are summarized, along with suggestions for future research areas.

  15. Modelling zirconium hydrides using the special quasirandom structure approach

    KAUST Repository

    Wang, Hao

    2013-01-01

    The study of the structure and properties of zirconium hydrides is important for understanding the embrittlement of zirconium alloys used as cladding in light water nuclear reactors. Simulation of the defect processes is complicated due to the random distribution of the hydrogen atoms. We propose the use of the special quasirandom structure approach as a computationally efficient way to describe this random distribution. We have generated six special quasirandom structure cells based on face centered cubic and face centered tetragonal unit cells to describe ZrH2-x (x = 0.25-0.5). Using density functional theory calculations we investigate the mechanical properties, stability, and electronic structure of the alloys. © the Owner Societies 2013.

  16. Delayed hydride cracking: theoretical model testing to predict cracking velocity

    International Nuclear Information System (INIS)

    Pressure tubes from Candu nuclear reactors as any other component manufactured with Zr alloys are prone to delayed hydride cracking. That is why it is important to be able to predict the cracking velocity during the component lifetime from parameters easy to be measured, such as: hydrogen concentration, mechanical and microstructural properties. Two of the theoretical models reported in literature to calculate the DHC velocity were chosen and combined, and using the appropriate variables allowed a comparison with experimental results of samples from Zr-2.5 Nb tubes with different mechanical and structural properties. In addition, velocities measured by other authors in irradiated materials could be reproduced using the model described above. (author)

  17. Noble-gas hydrides: new chemistry at low temperatures.

    Science.gov (United States)

    Khriachtchev, Leonid; Räsänen, Markku; Gerber, R Benny

    2009-01-20

    Noble-gas chemistry has been undergoing a renaissance in recent years, due in large part to noble-gas hydrides, HNgY, where Ng = noble-gas atom and Y = electronegative fragment. These molecules are exceptional because of their relatively weak bonding and large dipole moments, which lead to strongly enhanced effects of the environment, complexation, and reactions. In this Account, we discuss the matrix-isolation synthesis of noble-gas hydrides, their spectroscopic and structural properties, and their stabilities.This family of species was discovered in 1995 and now has 23 members that are prepared in noble-gas matrices (HXeBr, HKrCl, HXeH, HXeOH, HXeO, etc.). The preparations of the first neutral argon molecule, HArF, and halogen-free organic noble-gas molecules (HXeCCH, HXeCC, HKrCCH, etc.) are important highlights of the field. These molecules are formed by the neutral H + Ng + Y channel. The first addition reaction involving HNgY molecules was HXeCC + Xe + H --> HXeCCXeH, and this led to the first hydride with two noble-gas atoms (recently extended by HXeOXeH). The experimental synthesis of HNgY molecules starts with production of H and Y fragments in solid noble gas via the UV photolysis of suitable precursors. The HNgY molecules mainly form upon thermal mobilization of the fragments.One of the unusual properties of these molecules is the hindered rotation of some HNgY molecules in solid matrices; this has been theoretically modeled. HNgY molecules also have unusual solvation effects, and the H-Xe stretching mode shifts to higher frequencies (up to about 150 cm-1) upon interaction with other species.The noble hydrides have a new bonding motif: HNgY molecules can be represented in the form (H-Ng)+Y-, where (H-Ng)+ is mainly covalent, whereas the interaction between (HNg)+ and Y- is predominantly ionic. The HNgY molecules are highly metastable species representing high-energy materials. The decomposition process HNgY --> Ng + HY is always strongly exoergic

  18. Hydride Formation in Neutron Irradiated Material Under In Reactor Conditions

    International Nuclear Information System (INIS)

    The present is a brief summary of the three reports completed within the framework of the SPAR III project. The following is a resume of our aims, techniques used to achieve the objectives and conclusions attained under the guiding thread of the hydride formation in neutron irradiated zirconium alloys and other reactor in operating conditions. As is it known, under reactor operating conditions zirconium components go through transformations which affect their original microstructural and thermodynamical properties. Both concerns are starting points of many research lines for the zirconium alloys used in the nuclear power reactors. Regarding microstructural transformations, one of the most important topics is the phase stability of these alloys. To cite a well-known case, second phase particles of zircaloy-4 shown to be unstable under neutron radiation. Since such phases play a role in the corrosion rate control, this instability became a problem for high burnup fuel claddings design. Similar observations can be made about the β−Zr phase in the Zr-2.5Nb CANDU pressure tubes alloy. On the other hand, there are issues directly involved with thermodynamics, e.g., hydrogen behaviour and its role in the degradation processes of fuel assemblies and other zirconium alloys components, which showed to be affected by neutron radiation. Finally, applied stresses and thermal cycling are part of these operating conditions, which can be simulated performing experiments in situ which allows testing hydrogen solubility behaviour and hydride reorientation. In the context described above, the research topics proposed to SPAR III were aimed to improve the knowledge of these degradation processes. In this scheme, zircaloy-4 which remained more than ten years at full power operation and virgin unirradiated zirconium alloys were suited by the more improved micro analytical techniques to characterize microstructural transformations cited above

  19. Heat transfer characteristics of the metal hydride vessel based on the plate-fin type heat exchanger

    Science.gov (United States)

    Oi, Tsutomu; Maki, Kohei; Sakaki, Yoshinori

    Heat transfer characteristics of the metal hydride vessel based on the plate-fin type heat exchanger were investigated. Metal hydride beds were filled with AB 2 type hydrogen-storage alloy's particles, Ti 0.42Zr 0.58Cr 0.78Fe 0.57Ni 0.2Mn 0.39Cu 0.03, with a storage capacity of 0.92 wt.%. Heat transfer model in the metal hydride bed based on the heat transfer mechanism for packed bed proposed by Kunii and co-workers is presented. The time-dependent hydrogen absorption/desorption rate and pressure in the metal hydride vessel calculated by the model were compared with the experimental results. During the hydriding, calculated hydrogen absorption rates agreed with measured ones. Calculated thermal equilibrium hydrogen pressures were slightly lower than the measured hydrogen pressures at the inlet of metal hydride vessel. Taking account of the pressure gradient between the inlet of metal hydride vessel and the metal hydride bed, it is considered that this discrepancy is reasonable. During the dehydriding, there were big differences between the calculated hydrogen desorption rates and measured ones. As calculated hydrogen desorption rates were lower than measured ones, there were big differences between the calculated thermal equilibrium hydrogen pressures and the measured hydrogen pressures at the inlet of metal hydride vessel. It is considered that those differences are due to the differences of the heat transfer characteristics such as thermal conductivity of metal hydride particles and porosity between the assumed and actual ones. It is important to obtain the heat transfer characteristics such as thermal conductivity of metal hydride particles and porosity both during the hydriding and dehydriding to design a metal hydride vessel.

  20. Catalytic Radical Reduction in Aqueous Solution by a Ruthenium Hydride Intermediate.

    Science.gov (United States)

    Htet, Yamin; Tennyson, Andrew G

    2016-07-18

    Some manganese complexes can catalyze both antioxidant and pro-oxidant reactions, whereby the disparate reactivity modes are determined by the catalyst environment and afford distinct therapeutic effects. We recently reported the reduction of radicals in buffered aqueous solution catalyzed by a ruthenium complex with biologically relevant non-tertiary alcohols as terminal reductants. Mechanistic evidence is presented, indicating that this catalytic radical reduction is achieved by a Ru-hydride intermediate formed by β-hydride elimination from a Ru-alkoxide species. A similar mechanism and Ru-hydride intermediate was previously reported to kill cancer cells with catalytic pro-oxidant effects. Therefore, our demonstration of catalytic antioxidant effects by the same type of intermediate reveals new potential therapeutic strategies and applications for catalytic systems that form Ru-hydride intermediates. PMID:27254303

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

    CERN Document Server

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

    2002-01-01

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

  2. Hydride precipitation kinetics in Zircaloy-4 studied using synchrotron X-ray diffraction

    Science.gov (United States)

    Courty, Olivier F.; Motta, Arthur T.; Piotrowski, Christopher J.; Almer, Jonathan D.

    2015-06-01

    As a result of in-reactor corrosion during operation in nuclear reactors, hydrogen can enter the zirconium fuel cladding and precipitate as brittle hydride particles, which may reduce cladding ductility. Dissolved hydrogen responds to temperature gradients, resulting in transport and precipitation into cold spots so that the distribution of hydrides in the cladding is inhomogeneous. The hydrogen precipitation kinetics plays a strong role in the spatial distribution of the hydrides in the cladding. The precipitation rate is normally described as proportional to the supersaturation of hydrogen in solid solution. The proportionality constant, α2, for hydride precipitation in Zircaloy-4 is measured directly using in situ synchrotron X-Ray diffraction, at different temperatures and with three different initial hydrogen concentrations. The results validate the linear approximation of the phenomenological model and a near constant value of α2 = 4.5 × 10-4 s-1 was determined for the temperature range studied.

  3. The microstructure and hydriding characteristics of high temperature aged U-13 at.%Nb alloy

    Science.gov (United States)

    Ji, Hefei; Shi, Peng; Li, Ruiwen; Jiang, Chunli; Yang, Jiangrong; Hu, Guichao

    2015-09-01

    Niobium as alloying element significantly improves physical and chemical properties of metallic uranium, exhibiting great application potential in uranium alloy materials. The corrosion resistance performance as well as the internal alloy phase structure of uranium-niobium alloy is closely related to aging processes. Microstructure and hydriding characteristics of the 400 °C/9 h + 500 °C/2 h aged uranium-13 at.% niobium alloys (U-13 at.%Nb) were investigated from the point of view of relationship between the microstructure and growth of the hydriding areas. The microstructure, morphology and composition of the alloy phases before and after the hydriding were well characterized by the laser scanning confocal microscopy (LSCM), scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively. Experimental results indicated that the hydrogen preferentially reacted with the Nb-depleted phase α-like-U to form monolithic β-UH3Nbx, and the alloy microstructure played an important role in hydride growth.

  4. The two steps thermal decomposition of titanium hydride and two steps foaming of Al alloy

    Institute of Scientific and Technical Information of China (English)

    SHANG Jintang; HE Deping

    2005-01-01

    Two steps foaming (TSF) technique was proposed to prepare shaped Al alloy foam. Based on the thermal decomposition kinetics equation of titanium hydride, the relationship between two steps thermal decomposition kinetics of titanium hydride and two steps foaming Al alloy melt was studied. Two steps thermal decomposition curve of titanium hydride under increasing and constant temperature was calculated respectively. The hydrogen mass needed in the second foaming step was also calculated. Results showed that the hydrogen mass of the second thermal decomposition of titanium hydride is enough for the second foaming step in the condition of as-received Al melt foaming. Experimental and theoretical results indicate that two steps foaming technique can be used to prepare Al alloy foam with high porosity, shaped components and sandwich with Al alloy foam core.

  5. The formation and characteristics of hydride blisters in c.w. Zircaloy-2 pressure tubes

    International Nuclear Information System (INIS)

    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

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

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

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

  7. Dehydrogenation in lithium borohydride/conventional metal hydride composite based on a mutual catalysis

    DEFF Research Database (Denmark)

    Yu, X.B.; Shi, Qing; Vegge, Tejs;

    2009-01-01

    The dehydrogenation of LiBH4 ball-milled with hydrogenated 40Ti–15Mn–15Cr–30V alloy was investigated. It was found that there is a mutual catalysis between the two hydrides, lowering the temperature of hydrogen release from both hydrides. In the case of 1h milled LiBH4/40Ti–15Mn–15Cr–30V with a...

  8. The thermodynamics of hydride precipitation: the importance of entropy, enthalpy and disorder

    OpenAIRE

    Lumley, S. C.; Grimes, R. W.; Murphy, S. T.; Burr, P. A.; Chroneos, A.; Chard-Tucke, P. R.; Wenman, M. R.

    2014-01-01

    The thermodynamics of H/{\\alpha}-Zr solid solution and zirconium hydride phases were studied using density functional theory. Disorder in {\\zeta}, {\\gamma} and {\\delta} hydrides and solid solutions were modelled using a statistically significant number of randomly generated structures in combination with special quasi-random structures and solid solutions with a range of concentrations. This is used in conjunction with a calculation of thermodynamic parameters of the system, including the tem...

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

    CERN Document Server

    Awad, Zainab; Williams, David A

    2016-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-09-01

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

  11. Investigation of Lithium Metal Hydride Materials for Mitigation of Deep Space Radiation

    Science.gov (United States)

    Rojdev, Kristina; Atwell, William

    2016-01-01

    Radiation exposure to crew, electronics, and non-metallic materials is one of many concerns with long-term, deep space travel. Mitigating this exposure is approached via a multi-faceted methodology focusing on multi-functional materials, vehicle configuration, and operational or mission constraints. In this set of research, we are focusing on new multi-functional materials that may have advantages over traditional shielding materials, such as polyethylene. Metal hydride materials are of particular interest for deep space radiation shielding due to their ability to store hydrogen, a low-Z material known to be an excellent radiation mitigator and a potential fuel source. We have previously investigated 41 different metal hydrides for their radiation mitigation potential. Of these metal hydrides, we found a set of lithium hydrides to be of particular interest due to their excellent shielding of galactic cosmic radiation. Given these results, we will continue our investigation of lithium hydrides by expanding our data set to include dose equivalent and to further understand why these materials outperformed polyethylene in a heavy ion environment. For this study, we used HZETRN 2010, a one-dimensional transport code developed by NASA Langley Research Center, to simulate radiation transport through the lithium hydrides. We focused on the 1977 solar minimum Galactic Cosmic Radiation environment and thicknesses of 1, 5, 10, 20, 30, 50, and 100 g/cm2 to stay consistent with our previous studies. The details of this work and the subsequent results will be discussed in this paper.

  12. Influence of lanthanon hydride catalysts on hydrogen storage properties of sodium alanates

    Institute of Scientific and Technical Information of China (English)

    WU Zhe; CHEN Lixin; XIAO Xuezhang; FAN Xiulin; LI Shouquan; WANG Qidong

    2013-01-01

    NaAlH4 complex hydrides doped with lanthanon hydrides were prepared by hydrogenation of the ball-milled NaH/Al+xmol.% RE-H composites (RE=La,Ce; x=2,4,6) using NaHl and A1 powder as raw materials.The influence of lanthanon hydride catalysts on the hydriding and dehydriding behaviors of the as-synthesized composites were investigated.It was found that the composite doped with 2 mol.% La.H3.01 displayed the highest hydrogen absorption capacity of 4.78 wt.% and desorption capacity of 4.66wt.%,respectively.Moreover,the composite doped with 6 mol% CeH2.51 showed the best hydriding/dehydriding reaction kinetics.The proposed catalytic mechanism for reversible hydrogen storage properties of the composite was attributed to the presence of active LaH3.01 and CeH2.51 particles,which were scattering on the surface of NaH and A1 particles,acting as the catalytic active sites for hydrogen diffusion and playing an important catalytic role in the improved hydriding/dehydriding reaction.

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

    Institute of Scientific and Technical Information of China (English)

    高克玮; 王燕斌; 林志; 乔利杰; 褚武扬

    1999-01-01

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

  14. 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

  15. Development of delayed hydride cracking resistant-pressure tube

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Young Suk; Kwon, Sang Chul; Kim, S. S.; Yim, K. S

    2000-10-01

    For the first time, we demonstrate that the pattern of nucleation and growth of a DHC crack is governed by the precipitation of hydrides so that the DHC velocity and K{sub IH} are determined by an angle of the cracking plane and the hydride habit plane 10.7. Since texture controls the distribution of the 10.7 habit plane in Zr-2.5Nb pressure tube, we draw a conclusion that a textural change in Zr-2.5Nb tube from a strong tangential texture to the radial texture shall increase the threshold stress intensity factor, K{sub IH}, and decrease the delayed hydride cracking velocity. This conclusion is also verified by a complimentary experiment showing a linear dependence of DHCV and K{sub IH} with an increase in the basal component in the cracking plane. On the basis of the study on the DHC mechanism and the effect of manufacturing processes on the properties of Zr-2.5Nb tube, we have established a manufacturing procedure to make pressure tubes with improved DHC resistance. The main features of the established manufacturing process consist in the two step-cold pilgering process and the intermediate heat treatment in the {alpha} + {beta} phase for Zr-2.5Nb alloy and in the {alpha} phase for Zr-1Nb-1.2Sn-0.4Fe alloy. The manufacturing of DHC resistant-pressure tubes of Zr-2.5Nb and Zr-1N-1.2Sn-0.4Fe was made in the ChMP zirconium plant in Russia under a joint research with Drs. Nikulina and Markelov in VNIINM (Russia). Zr-2.5Nb pressure tube made with the established manufacturing process has met all the specification requirements put by KAERI. Chracterization tests have been jointly conducted by VNIINM and KAERI. As expected, the Zr-2.5Nb tube made with the established procedure has improved DHC resistance compared to that of CANDU Zr-2.5Nb pressure tube used currently. The measured DHC velocity of the Zr-2.5Nb tube meets the target value (DHCV <5x10{sup -8} m/s) and its other properties also were equivalent to those of the CANDU Zr-2.5Nb tube used currently. The Zr-1Nb-1

  16. 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

  17. Improved Electrochemical Performance of Surface-Modified Metal Hydride Electrodes

    Institute of Scientific and Technical Information of China (English)

    YANG Kai; WU Feng; CHEN Shi; ZHANG Cun-zhong

    2005-01-01

    A novel plating process was applied to the surface modification of the metal hydride (MH) electrode of the MH/Ni batteries. The electrode was plated with a thin nickel film about 0.1 μm thick by using multi-arc ion plating technique. The X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscope (SEM) were used to analyze the electrodes. Influence of the surface modification on the performance of the MH/Ni batteries was studied. It is shown that the surface modification could enhance the electrode conductivity and decrease the batteries ohimic resistance by 28.2 %. After surface modification, the discharge capacity of modification also improves the cyclic durability of the batteries. The inner pressure of the batteries with modified electrode during overcharging is much lower than that with unmodified electrode. The experimental results demonstrate that this process is an effective way for the surface modification of the electrode of MH/Ni batteries.

  18. Superhalogens as Building Blocks of Complex Hydrides for Hydrogen Storage

    CERN Document Server

    Srivastava, Ambrish Kumar

    2016-01-01

    Superhalogens are species whose electron affinity (EA) or vertical detachment energy (VDE) exceed to those of halogen. These species typically consist of a central electropositive atom with electronegative ligands. The EA or VDE of species can be further increased by using superhalogen as ligands, which are termed as hyperhalogen. Having established BH4- as a superhalogen, we have studied BH4-x(BH4)x- (x = 1 to 4) hyperhalogen anions and their Li-complexes, LiBH4-x(BH4)x using density functional theory. The VDE of these anions is larger than that of BH4-, which increases with the increase in the number of peripheral BH4 moieties (x). The hydrogen storage capacity of LiBH4-x(BH4)x complexes is higher but binding energy is smaller than that of LiBH4, a typical complex hydride. The linear correlation between dehydrogenation energy of LiBH4-x(BH4)x complexes and VDE of BH4-x(BH4)x- anions is established. These complexes are found to be thermodynamically stable against dissociation into LiBH4 and borane. This stud...

  19. Unloading Effect on Delayed Hydride Cracking in Zirconium Alloys

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Young Suk; Kim, Sung Soo [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2010-05-15

    It is well-known that a tensile overload retards not only the crack growth rate (CGR) in zirconium alloys during the delayed hydride cracking (DHC) tests but also the fatigue crack growth rate in metals, the cause of which is unclear to date. A considerable decrease in the fatigue crack growth rate due to overload is suggested to occur due either to the crack closure or to compressive stresses or strains arising from unloading of the overload. However, the role of the crack closure or the compressive stress in the crack growth rate remains yet to be understood because of incomplete understanding of crack growth kinetics. The aim of this study is to resolve the effect of unloading on the CGR of zirconium alloys, which comes in last among the unresolved issues as listed above. To this end, the CGRs of the Zr-2.5Nb tubes were determined at a constant temperature under the cyclic load with the load ratio, R changing from 0.13 to 0.66 where the extent of unloading became higher at the lower R. More direct evidence for the effect of unloading after an overload is provided using Simpson's experiment investigating the effect on the CGR of a Zr-2.5Nb tube of the stress states of the prefatigue crack tip by unloading or annealing after the formation of a pre-fatigue crack

  20. Synthesis and Hydrogen Desorption Properties of Aluminum Hydrides.

    Science.gov (United States)

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

    2016-03-01

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

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

    Science.gov (United States)

    Dzierlenga, Michael; Antoniou, Dimitri; Schwartz, Steven

    2015-03-01

    The mechanisms involved in enzymatic hydride transfer have been studies for years but questions remain, due to the difficulty in determining the participation of protein dynamics and quantum effects, especially 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 lactate dehydrogenase (LDH). Calculation of the work applied to the hydride during the reaction allows for observation of the change in barrier height due to inclusion of quantum effects. Additionally, the same calculations were performed using deuterium as the transferring particle to validate our methods with experimentally measured kinetic isotope effects. The change in barrier height in YADH upon inclusion of quantum effects is indicative of a zero-point energy contribution, and is evidence that the protein mediates a near-barrierless transfer of the rate-limiting hydride. Calculation of kinetic isotope effects using the average difference in barrier between hydride and deuteride agreed well with experimental results. The authors acknowledge the support of the National Institutes of Health Grants GM068036 and GM102226.

  2. 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.

  3. Cool-down induced hydride reorientation of hydrogen-charged Zirconium alloy cladding tubes

    International Nuclear Information System (INIS)

    250 and 500ppm hydrogen-charged Zirconium alloy tubes were employed to investigate hydride reorientation behaviors when they were cool down from 400 to 300, 200degC and room temperature with various cooling rates of 0.3, 2.0, 4.0, 7.0 and 15.0degC/min under a tensile hoop stress of 150MPa. These cool-down tests indicate that the slower cooling rate and the lower terminal cool-down temperature produced the more hydrides precipitated along with the larger fraction and the longer length of radial hydrides. These phenomena may be explained by terminal solid solubility of hydrogen for dissolution and precipitation and cooling rate-dependent hydride nucleation and growth rates. On the other hand, a dramatic decrease of ultimate tensile strength and plastic strain of the cool-down tested specimens may be explained by the amount of the radial hydrides precipitated during the cool-down process. (author)

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

    International Nuclear Information System (INIS)

    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)

  5. Tandem olefin metathesis/hydrogenation at ambient temperature: activation of ruthenium carbene complexes by addition of hydrides.

    Science.gov (United States)

    Schmidt, Bernd; Pohler, Michael

    2003-07-21

    Sodium hydride activates ruthenium carbene complexes to catalyze hydrogenation reactions subsequent to ring closing olefin metathesis. Under these conditions, hydrogenation of cyclopentenols proceeds smoothly at ambient temperature and under 1 atm of hydrogen in toluene. An alternative protocol was developed that involves the formation of hydrogen in situ by reaction of excess sodium hydride with protic functional groups and water. PMID:12956069

  6. Preparation of Uranium Powder having Reactive Shape using Uranium Hydridation

    International Nuclear Information System (INIS)

    The accident tolerance of the LWR fuel has become a primary matter of concern. So, it is indispensable to develop the innovative nuclear fuel material concepts and technologies which can overcome degradation of fuel safety and integrity. Uranium nitride fuel has been proposed as a potential fuel material for advanced nuclear reactors because nitride fuel has the advantages of both metallic and oxide fuels. That is, the high melting point, high uranium density, and high thermal conductivity are the representative merits of nitride fuel. Nitride fuel is also considered as a fuel material for the accident tolerant fuel of current LWRs to compensate for the decrease in fissile fuel material caused by adopting a thickened cladding such as SiC composites. However, nitride fuel has a critical disadvantage of a serious reaction with water at a typical LWR condition. Bulk uranium nitride is known to be dissolved in water at a temperature above 230 .deg. C. Uranium nitride powder is more unstable and reacts with water at about 150 .deg. C. Therefore, the water-proof nitride fuel must be developed to apply to current LWRs. Several strategies to prevent or reduce the reaction of nitride fuel with water have been suggested. KAERI is developing uranium nitride-oxide composite fuel pellet that is expected to have higher fuel performance and lower water reactivity. In the development of the fabrication technologies of uranium based composite fuel pellet, uranium nitride powder should be prepared, first. We have considered a simple reaction method to fabricate uranium nitride powders directly from metal uranium powders. Also, to create reactive uranium powder with nitrogen, it is applied that the uranium powder is pretreated in the hydrogen atmosphere. In this study, to investigate the behavior of the uranium powder hydriding process, thermal analysis tests were performed

  7. Optical hydrogen sensors based on metal-hydrides

    Science.gov (United States)

    Slaman, M.; Westerwaal, R.; Schreuders, H.; Dam, B.

    2012-06-01

    For many hydrogen related applications it is preferred to use optical hydrogen sensors above electrical systems. Optical sensors reduce the risk of ignition by spark formation and are less sensitive to electrical interference. Currently palladium and palladium alloys are used for most hydrogen sensors since they are well known for their hydrogen dissociation and absorption properties at relatively low temperatures. The disadvantages of palladium in sensors are the low optical response upon hydrogen loading, the cross sensitivity for oxygen and carbon, the limited detection range and the formation of micro-cracks after some hydrogen absorption/desorption cycles. In contrast to Pd, we find that the use of magnesium or rear earth bases metal-hydrides in optical hydrogen sensors allow tuning of the detection levels over a broad pressure range, while maintaining a high optical response. We demonstrate a stable detection layer for detecting hydrogen below 10% of the lower explosion limit in an oxygen rich environment. This detection layer is deposited at the bare end of a glass fiber as a micro-mirror and is covered with a thin layer of palladium. The palladium layer promotes the hydrogen uptake at room temperature and acts as a hydrogen selective membrane. To protect the sensor for a long time in air a final layer of a hydrophobic fluorine based coating is applied. Such a sensor can be used for example as safety detector in automotive applications. We find that this type of fiber optic hydrogen sensor is also suitable for hydrogen detection in liquids. As example we demonstrate a sensor for detecting a broad range of concentrations in transformer oil. Such a sensor can signal a warning when sparks inside a high voltage power transformer decompose the transformer oil over a long period.

  8. Metal hydride heat pump engineering demonstration and evaluation model

    Science.gov (United States)

    Lynch, Franklin E.

    1993-01-01

    Future generations of portable life support systems (PLSS's) for space suites (extravehicular mobility units or EMU's) may require regenerable nonventing thermal sinks (RNTS's). For purposes of mobility, a PLSS must be as light and compact as possible. Previous venting PLSS's have employed water sublimators to reject metabolic and equipment heat from EMU's. It is desirable for long-duration future space missions to minimize the use of water and other consumables that need to be periodically resupplied. The emission of water vapor also interferes with some types of instrumentation that might be used in future space exploration. The test article is a type of RNTS based on a metal hydride heat pump (MHHP). The task of reservicing EMU's after use must be made less demanding in terms of time, procedures, and equipment. The capability for quick turnaround post-EVA servicing (30 minutes) is a challenging requirement for many of the RNTS options. The MHHP is a very simple option that can be regenerated in the airlock within the 30 minute limit by the application of a heating source and a cooling sink. In addition, advanced PLSS's must provide a greater degree of automatic control, relieving astronauts of the need to manually adjust temperatures in their liquid cooled ventilation garments (LCVG's). The MHHP includes automatic coolant controls with the ability to follow thermal load swings from minimum to maximum in seconds. The MHHP includes a coolant loop subsystem with pump and controls, regeneration equipment for post-EVA servicing, and a PC-based data acquisition and control system (DACS).

  9. Mechanism of negative hydrogen ion emission from heated saline hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Kawano, Hiroyuki; Serizawa, Naoshi; Takeda, Makiko; Hasegawa, Seiji [Ehime Univ., Matsuyama (Japan). Faculty of Science

    1997-02-01

    To find a clue to the mechanism of negative hydrogen ion emission from a heated sample ({approx}10 mg) of powdery saline hydride (LiH or CaH{sub 2}) deposited on a molybdenum ribbon ({approx}0.1 cm{sup 2}), both the ionic and electronic emission currents were measured as a function of sample temperature ({approx}700 - 800 K), thereby yielding {approx}10{sup -15} - 10{sup -12} A of H{sup -} after mass analysis and {approx}10{sup -7} - 10{sup -5} A of thermal electron. Thermophysical analysis of these data indicates that the desorption energy (E{sup -}) of H{sup -} and work function ({phi}) of the emitting sample surface are 5.1 {+-} 0.3 and 3.1 {+-} 0.2 eV for LiH, respectively, while E{sup -} is 7.7 {+-} 0.3 eV and {phi} is 5.0 {+-} 0.2 eV for CaH{sub 2}. Thermochemical analysis based on our simple model on the emissions indicates that the values of E{sup -} - {phi} are 2.35 and 2.31 eV for LiH and CaH{sub 2}, respectively, which are in fair agreement with the respective values (2.1 {+-} 0.3 and 2.6 {+-} 0.3 eV) determined experimentally. This agreement indicates that the emission of H{sup -} is reasonably explained by our model from the viewpoint of reaction energy. (author)

  10. Hydrogen storage: hydrogen as a hydride. 1974-May, 1980 (citations from the NTIS Data Base). Report for 1974-May 80. [135 abstracts

    Energy Technology Data Exchange (ETDEWEB)

    Cavagnaro, D.M.

    1980-06-01

    The bibliography covers hydrogen storage as a hydride. Topics include the chemical and physical properties of the hydride, and how useful it may be for hydrogen storage. Also considered is the conversion of hydrogen to a hydride and the conversion back to hydrogen. (This updated bibliography contains 135 abstracts, 14 of which are new entries to the previous edition.)

  11. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Van Blarigan, Peter; Shugard, Andrew D.; Walters, R. Tom (Savannah River National Labs, Aiken, SC)

    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.

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

    Science.gov (United States)

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

    2015-12-01

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

  14. 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. PMID:26638824

  15. Measured and calculated fast neutron spectra in a depleted uranium and lithium hydride shielded reactor

    Science.gov (United States)

    Lahti, G. P.; Mueller, R. A.

    1973-01-01

    Measurements of MeV neutron were made at the surface of a lithium hydride and depleted uranium shielded reactor. Four shield configurations were considered: these were assembled progressively with cylindrical shells of 5-centimeter-thick depleted uranium, 13-centimeter-thick lithium hydride, 5-centimeter-thick depleted uranium, 13-centimeter-thick lithium hydride, 5-centimeter-thick depleted uranium, and 3-centimeter-thick depleted uranium. Measurements were made with a NE-218 scintillation spectrometer; proton pulse height distributions were differentiated to obtain neutron spectra. Calculations were made using the two-dimensional discrete ordinates code DOT and ENDF/B (version 3) cross sections. Good agreement between measured and calculated spectral shape was observed. Absolute measured and calculated fluxes were within 50 percent of one another; observed discrepancies in absolute flux may be due to cross section errors.

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

    Institute of Scientific and Technical Information of China (English)

    CHEN Weidong; WANG Lijun; HAN Lin; CHEN Song

    2008-01-01

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

  17. Behavior of Fatigue Crack Propagation for Grade 2 Titanium on the Hydride Formation

    International Nuclear Information System (INIS)

    Fatigue crack growth tests were carried out to investigate the crack growth behavior of hydrided ASTM Grade 2 Titanium plate at 25 .deg. C and 300 .deg. C. The hydride in the α type titanium was formed by ingressing H2 gas(100-300mbar) at 300 .deg. C-500 .deg. C. Fatigue crack growth rates of the Ti specimens at 300 .deg. C were higher than the growth rates at room temperature. The fatigue crack growth rates along the rolling direction were always higher than those of along the transverse rolling direction. The fatigue crack growth rate of hydrogen charged Ti was strongly dependent on the crack plane orientation in the rolled sheet and the arrangement of hydrides relative to the crack growth direction

  18. Influence of the crack-tip hydride concentration on the fracture toughness of Zircaloy-4

    Energy Technology Data Exchange (ETDEWEB)

    Bertolino, G. [LMS, CNRS UMR7649, Ecole Polytechnique, 91128 Palaiseau cedex (France)]. E-mail: bertolin@cab.cnea.gov.ar; Perez Ipina, J. [CONICET (Argentina); Universidad Nacional del Comahue, 8300 Neuquen (Argentina); Meyer, G. [Centro Atomico Bariloche, CNEA, 8400 Bariloche (Argentina); CONICET (Argentina)

    2006-01-01

    The influence of a hydrogen concentration gradient at the crack-tip and hydride platelet orientation on the fracture toughness, fracture mode and micromechanisms of a Zircaloy-4 commercial alloy was studied. Fracture toughness was measured on CT specimens and the analysis was performed in terms of J-integral resistance curves at temperatures ranging from 293 to 473 K. Fracture toughness results of specimens containing higher hydrides concentration near the crack-tip region, preferentially orientated in the crack plane, were compared to those obtained from specimens with a homogeneous hydrogen distribution and different platelet orientation; specimens were obtained by charging them in loaded and unloaded condition, respectively. Changes on both macroscopic and microscopic fracture behaviour were observed at temperatures ranging from 293 to 343 K, and the results show the relevance of both hydride concentration and platelet orientation. The existence of a ductile-to-brittle transition is discussed at the light of these new results.

  19. Computer simulation of the reflection of hydrogen and the sputtering of hydrogen from metal hydrides

    International Nuclear Information System (INIS)

    Reflection of 0.1 to 2 keV H atoms from Ti, Fe and their 'metal hydrides', together with the H sputtered from the latter, have been calculated using the binary collision cascade program MARLOWE. The fraction of particles and energy reflected is found to decrease with increasing hydrogen content of the metal hydride and this decrease is independent of the incident ion energy. It is found that the heavy metal atoms of the metal hydride are responsible for the reflection and that most of the sputtering is produced by the reflected ion as it exists through the surface layer. It is also found that tritium ions sputter H from 'FeH' much more effectively than H ions sputter T from 'FeT'. (Auth.)

  20. Computer simulation of the reflection of hydrogen and the sputtering of hydrogen from metal hydrides

    International Nuclear Information System (INIS)

    Reflection of 0.1 to 2 keV H atoms from Ti, Fe and their ''metal hydrides,'' together with the H sputtered from the latter, have been calculated using the binary collision cascade program MARLOWE. The fraction of particles and energy reflected is found to decrease with increasing hydrogen content of the metal hydride and this decrease is independent of the incident ion energy. It is found that the heavy metal atoms of the metal hydride are responsible for the reflection and that most of the sputtering is produced by the reflected ion as it exits through the surface layer. It is also found that tritium ions sputter H from ''FeH'' much more effectively than H ions sputter T from ''FeT.''

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

    Directory of Open Access Journals (Sweden)

    Hiroyuki Oguchi

    2015-09-01

    Full Text Available 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 RRMS of ∼0.4 nm.

  2. Structure and Dynamics of Perovskite Hydrides: AMgH3, A=Na,K,Rb

    Energy Technology Data Exchange (ETDEWEB)

    Fornari, M. [Central Michigan University, Mt. Pleasant; Subedi, Alaska P [ORNL; Singh, David J [ORNL

    2007-01-01

    We report density functional studies of the structure and dynamics of NaMgH{sub 3}, KMgH{sub 3}, and RbMgH{sub 3} in the cubic perovskite structure as well as the corresponding fluorides and the alloy (Na,Li)MgH{sub 3}. The hydrides are ionic materials with structural properties very similar to fluorides. However, even though the structures of the hydrides and fluorides are very similar, we find that the dynamics can be quite different. We ascribe these differences to breathing of the hydride ion. This is also reflected in a reduced tendency toward Li off-centering in (Na,Li)MgH{sub 3}.

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

    Directory of Open Access Journals (Sweden)

    C A Stitt

    Full Text Available 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.

  4. Compensation Effect in the Hydrogenation/Dehydrogenation Kinetics of Metal Hydrides

    DEFF Research Database (Denmark)

    Andreasen, A.; Vegge, T.; Pedersen, Allan Schrøder

    2005-01-01

    The possible existence of a compensation effect, i.e. concurrent changes in activation energy and prefactor, is investigated for the hydrogenation and dehydrogenation kinetics of metal hydrides, by analyzing a series of reported kinetic studies on Mg and LaNi5 based hydrides. For these systems, we...... find a clear linear relation between apparent prefactors and apparent activation energies, as obtained from an Arrhenius analysis, indicating the existence of a compensation effect. Large changes in apparent activation energies in the case of Mg based hydrides are rationalized in terms of a dependency...... of observed apparent activation energy on the degree of surface oxidation, i.e., a physical effect. On the other hand, we find the large concurrent changes in apparent prefactors to be a direct result of the Arrhenius analysis. Thus, we find the observed compensation effect to be an artifact of the data...

  5. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Gorman, R.; Moritz, P.

    1978-05-01

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

  7. Digestion and preparation methods of different samples determine elements produced hydride generation

    International Nuclear Information System (INIS)

    The aim of this work is to explain the principle of hydride generation technique, which is another technique of atomic absorption spectrometry, in addition to flame and graphite techniques. This technique is used to determine some metals and nonmetals (Se, Sn, Te, Sb, Bi, AS, Hg ) which produce volatile compounds in their reactions. The study focuses on the analytical capabilities of the hydride generation technique, the principle of hydride generation process, the interferences that affect the analysis process (spectra interference, chemical interference, kinetic interference, oxidation state interference, gas layer interference) and the methods to overcome these interferences. The working steps of the technique have been reported, finally some experimental work has been performed on different kind of samples such as: waste, tripolyphosphate, volcanic rock and phosphogypsum to determine mercury and blood sample to determine arsenic. (Authors)

  8. Impedance and self-discharge mechanism studies of nickel metal hydride batteries for energy storage applications

    Science.gov (United States)

    Zhu, Wenhua; Zhu, Ying; Tatarchuk, Bruce

    2013-04-01

    Nickel metal hydride battery packs have been found wide applications in the HEVs (hybrid electric vehicles) through the on-board rapid energy conservation and efficient storage to decrease the fossil fuel consumption rate and reduce CO2 emissions as well as other harmful exhaust gases. In comparison to the conventional Ni-Cd battery, the Ni-MH battery exhibits a relatively higher self-discharge rate. In general, there are quite a few factors that speed up the self-discharge of the electrodes in the sealed nickel metal hydride batteries. This disadvantage eventually reduces the overall efficiency of the energy conversion and storage system. In this work, ac impedance data were collected from the nickel metal hydride batteries. The self-discharge mechanism and battery capacity degradation were analyzed and discussed for further performance improvement.

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

    Science.gov (United States)

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

    2016-06-01

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

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

    Science.gov (United States)

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

    2016-08-01

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

  11. Study of hydride blisters in Zr-alloy using neutron tomography

    International Nuclear Information System (INIS)

    Highlights: ► We have established neutron tomography as a potential tool for the study of blister formation. ► Location, size and hydride distribution in the vicinity of blisters has been imaged. ► Hydrogen concentration up to 25 wppm in the reconstructed images has been detected. ► Linear relation between mode of image histogram and hydrogen concentration has been found. ► Spatial in-homogeneity of hydride distribution has also been identified in tomographic images. - Abstract: Formation of hydride blisters in Zircaloy pressure tubes of pressurized heavy water reactor (PHWR) is a major life limiting factor which hinders the safe and uninterrupted operation of the reactor. Nondestructive detection and evaluation of location and size of these blisters as well as hydride distribution in the matrix surrounding them may help in damage quantification and residual life extension. In this article we present the neutron tomography studies carried out on simulated hydride blister samples grown on Zircaloy tubes. Characterization on samples having various levels of hydrogen concentrations were also carried out for quantification of the detectability of our neutron tomography system. We could identify the spatial in-homogeneity of hydride concentration present in the samples. Quantitatively hydrogen concentration difference up to 25 wppm has been observed experimentally and calibrated against image intensity in the reconstructed image. This study establishes neutron tomography as a potential non-destructive evaluation tool for the estimation of the severity of damage in the integrity of the pressure tubes and provides valuable information about kinetics of blister formation.

  12. Ultrasonic estimation of hydride degradation of zirconium pressure tubes of RBMK fuel channel

    International Nuclear Information System (INIS)

    Fuel channels of nuclear reactors, which are major structural elements of a reactor core, have to meet strict requirements in terms of operational reliability. The middle part of the fuel channel, located in a graphite stack, is a tube made of a zirconium-2.5% niobium alloy. However, zirconium alloys can pick up hydrogen during operation as a consequence of corrosion reaction with water. Hydrogen redistributes easily at elevated temperatures migrating down a temperature or concentration gradient and up a stress gradient. When the terminal solid solubility is exceeded in a component such as a pressure tube that is highly stressed for long periods of time, delayed hydride cracking failures may occur. To estimate degradation of the zirconium alloy in the presence of hydrides, predetermined amounts of hydrogen were added to the sections of the fuel channel tubes by electrolytic deposition of a layer of hydride on the surface of the pressure tube material followed by dissolving the hydride layer by diffusion annealing at an elevated temperature. For estimation of the concentration of zirconium hydride platelets in the zirconium alloy test samples ultrasonic testing methods were proposed. The first method is based on precise measurement of velocity of longitudinal and shear wave at different directions and the second is based on the investigation of high frequency ultrasonic signals backscattered in a focal zone of an ultrasonic transducer. The experimental investigations were performed on the zirconium alloy samples of different concentration of hydrides in the immersion tank at a room temperature. The results obtained on testing samples using different excitation conditions and different types of ultrasonic waves are presented. (orig.)

  13. Carbon enhanced hydriding of oxidized U-0.1wt%Cr surfaces

    Science.gov (United States)

    Shamir, N.; Schweke, D.; Rubin, A.; Livneh, T.; Zalkind, S.

    2010-03-01

    The effect of deposited amorphous carbon on the reactivity of uranium towards hydridization has been investigated by means of optical (HSM), electron (SEM), Raman scattering and atomic force (AFM) microscopies. Clear preference was found towards hydrogen attack on the carbon covered area as mostly manifested by the formation of hollow blister-like hydrides with average height of ~1μm, and crust of few hundreds of nm. NOTE: As a result of an inadvertent AN2009 editorial error that led to publication of non-finalized version the PDF was replaced with the correct version on 16 September 2010. The original PDF can be found in the supplementary data.

  14. Ruthenium hydride-promoted dienyl isomerization: access to highly substituted 1,3-dienes.

    Science.gov (United States)

    Clark, Joseph R; Griffiths, Justin R; Diver, Steven T

    2013-03-01

    Ruthenium hydrides were found to promote the positional isomerization of 1,3-dienes into more highly substituted 1,3-dienes in a stereoconvergent manner. The reaction can be conducted in one pot starting with terminal alkynes and alkenes by triggering decomposition of the Grubbs catalyst into a ruthenium hydride, which promotes the dienyl isomerization. The presence of an alcohol additive plays a helpful role in the reaction, significantly increasing the chemical yields. Mechanistic studies are consistent with hydrometalation of the geminally substituted alkene of the 1,3-diene and transit of the ruthenium atom across the diene framework via a π-allylruthenium intermediate. PMID:23427813

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

    Science.gov (United States)

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

    2015-12-21

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

  16. 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

  17. A semi-empirical approach to accurate standard enthalpies of formation for solid hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Klaveness, A. [Department of Chemistry, University of Oslo, P.O. Box 1033, Blindern, N-0315 Oslo (Norway)], E-mail: arnekla@kjemi.uio.no; Fjellvag, H.; Kjekshus, A.; Ravindran, P. [Department of Chemistry, University of Oslo, P.O. Box 1033, Blindern, N-0315 Oslo (Norway); Swang, O. [SINTEF Materials and Chemistry, P.O. Box 124, Blindern, N-0314 Oslo (Norway)

    2009-02-05

    A semi-empirical method for estimation of enthalpies of formation of solid hydrides is proposed. The method is named Ionic for short. By combining experimentally known enthalpies of formation for simple hydrides and reaction energies computed using band-structure density functional theory (DFT) methods, startling accurate results can be achieved. The approach relies on cancellation of errors when comparing DFT energies for systems with similar electronic structures. The influence of zero-point energies, polaritons, and vibrational excitations on the results has been examined and found to be minor.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-02-15

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

  19. Effects of Hf on thermal and mechanical properties of Zr hydrides

    International Nuclear Information System (INIS)

    The polycrystalline fine bulk samples of δ-phase Zr hydrides with various Hf contents were prepared and their thermal and mechanical properties were investigated. In the temperature range from room temperature to 973 K, the phase states were examined by high-temperature X-ray diffraction and thermogravimetry/differential thermal analyses. In the temperature range from room temperature to 673 K, the coefficient of linear thermal expansion, specific heat capacity, and thermal conductivity were evaluated. The Vickers hardness and sound velocity were measured at room temperature, and the elastic modulus was evaluated. The effects of Hf on the thermal and mechanical properties of Zr hydrides were studied. (author)

  20. Investigations of the structural stability of metal hydride composites by in-situ neutron imaging

    Science.gov (United States)

    Herbrig, Kai; Pohlmann, Carsten; Gondek, Łukasz; Figiel, Henryk; Kardjilov, Nikolay; Hilger, André; Manke, Ingo; Banhart, John; Kieback, Bernd; Röntzsch, Lars

    2015-10-01

    Metal hydride composites (MHC) with expanded natural graphite (ENG) exhibiting enhanced thermal conductivity and reduced porosity compared to metal hydride powders can enable a reversible, compact and safe way for hydrogen storage. In this study, neutron imaging during cyclic hydrogenation was utilized to investigate the structural stability and the spatial-temporal hydrogen concentration of application-oriented MHC with 40 mm in diameter compared to a loose metal hydride powder. In particular, swelling and shrinking effects of a radially confined MHC which could freely expand upwards were studied. It was found that the loose powder bed was easily torn apart during dehydrogenation, which leads to increased thermal resistance within the hydride bed. In contrast, the thermal resistance between MHC and container wall was minimized since the initial gap closes during initial hydrogenation and does not reopen thereafter. Further cyclic hydrogenation caused MHC volume changes, i.e. an almost reversible swelling/shrinking (so-called "MHC breathing"). Moreover, neutron imaging allowed for the observation of reaction fronts within the MHC and the powder bed that are governed by the heat transfer.

  1. Synthesis and Characterization of Metal Hydride/Carbon Aerogel Composites for Hydrogen Storage

    Directory of Open Access Journals (Sweden)

    Kuen-Song Lin

    2012-01-01

    Full Text Available Two materials currently of interest for onboard lightweight hydrogen storage applications are sodium aluminum hydride (NaAlH4, a complex metal hydride, and carbon aerogels (CAs, a light porous material connected by several spherical nanoparticles. The objectives of the present work have been to investigate the synthesis, characterization, and hydrogenation behavior of Pd-, Ti- or Fe-doped CAs, NaAlH4, and MgH2 nanocomposites. The diameters of Pd nanoparticles onto CA’s surface and BET surface area of CAs were 3–10 nm and 700–900 m2g−1, respectively. The H2 storage capacity of metal hydrides has been studied using high-pressure TGA microbalance and they were 4.0, 2.7, 2.1, and 1.2 wt% for MgH2-FeTi-CAs, MgH2-FeTi, CAs-Pd, and 8 mol% Ti-doped NaAlH4, respectively, at room temperature. Carbon aerogels with higher surface area and mesoporous structures facilitated hydrogen diffusion and adsorption, which accounted for its extraordinary hydrogen storage phenomenon. The hydrogen adsorption abilities of CAs notably increased after inclusion of metal hydrides by the “hydrogen spillover” mechanisms.

  2. Herschel/HIFI detections of hydrides towards AFGL 2591: Envelope emission versus tenuous cloud absorption

    NARCIS (Netherlands)

    S. Bruderer; A.O. Benz; E.F. van Dishoeck; M. Melchior; S.D. Doty; F. van der Tak; P. Stäuber; S.F. Wampfler; C. Dedes; U.A. Yıldız; L. Pagani; T. Giannini; T. de Graauw; N. Whyborn; D. Teyssier; W. Jellema; R. Shipman; R. Schieder; N. Honingh; E. Caux; W. Bächtold; A. Csillaghy; C. Monstein; R. Bachiller; A. Baudry; M. Benedettini; E. Bergin; P. Bjerkeli; G.A. Blake; S. Bontemps; J. Braine; P. Caselli; J. Cernicharo; C. Codella; F. Daniel; A.M. Di Giorgio; C. Dominik; P. Encrenaz; M. Fich; A. Fuente; J.R. Goicoechea; F. Helmich; G.J. Herczeg; F. Herpin; M.R. Hogerheijde; T. Jacq; D. Johnstone; J.K. Jørgensen; L.E. Kristensen; B. Larsson; D. Lis; R. Liseau; M. Marseille; C. McCoey; G. Melnick; D. Neufeld; B. Nisini; M. Olberg; B. Parise; J.C. Pearson; R. Plume; C. Risacher; J. Santiago-García; P. Saraceno; R. Shipman; M. Tafalla; T.A. van Kempen; R. Visser; F. Wyrowski

    2010-01-01

    The Heterodyne Instrument for the Far Infrared (HIFI) onboard the Herschel Space Observatory allows the first observations of light diatomic molecules at high spectral resolution and in multiple transitions. Here, we report deep integrations using HIFI in different lines of hydrides towards the high

  3. Herschel/HIFI detections of hydrides towards AFGL 2591. Envelope emission versus tenuous cloud absorption

    DEFF Research Database (Denmark)

    Bruderer, S.; Benz, A. O.; van Dishoeck, E. F.;

    2010-01-01

    The Heterodyne Instrument for the Far Infrared (HIFI) onboard the Herschel Space Observatory allows the first observations of light diatomic molecules at high spectral resolution and in multiple transitions. Here, we report deep integrations using HIFI in different lines of hydrides towards the h...

  4. 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...

  5. Aluminum-titanium hydride-boron carbide composite provides lightweight neutron shield material

    Science.gov (United States)

    Poindexter, A. M.

    1967-01-01

    Inexpensive lightweight neutron shield material has high strength and ductility and withstands high internal heat generation rates without excessive thermal stress. This composite material combines structural and thermal properties of aluminum, neutron moderating properties of titanium hydride, and neutron absorbing characteristics of boron carbide.

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

    Science.gov (United States)

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

    2016-08-01

    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 (σ2/σ1 = 0) to "near-equibiaxial" tension (σ2/σ1 = 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.

  7. A PROTOTYPE FOUR INCH SHORT HYDRIDE (FISH) BED AS A REPLACEMENT TRITIUM STORAGE BED

    Energy Technology Data Exchange (ETDEWEB)

    Klein, J.; Estochen, E.; Shanahan, K.; Heung, L.

    2011-02-23

    The Savannah River Site (SRS) tritium facilities have used 1st generation (Gen1) metal hydride storage bed assemblies with process vessels (PVs) fabricated from 3 inch nominal pipe size (NPS) pipe to hold up to 12.6 kg of LaNi{sub 4.25}Al{sub 0.75} metal hydride for tritium gas absorption, storage, and desorption for over 15 years. The 2nd generation (Gen2) of the bed design used the same NPS for the PV, but the added internal components produced a bed nominally 1.2 m long, and presented a significant challenge for heater cartridge replacement in a footprint limited glove-box. A prototype 3rd generation (Gen3) metal hydride storage bed has been designed and fabricated as a replacement candidate for the Gen2 storage bed. The prototype Gen3 bed uses a PV pipe diameter of 4 inch NPS so the bed length can be reduced below 0.7 m to facilitate heater cartridge replacement. For the Gen3 prototype bed, modeling results show increased absorption rates when using hydrides with lower absorption pressures. To improve absorption performance compared to the Gen2 beds, a LaNi{sub 4.15}Al{sub 0.85} material was procured and processed to obtain the desired pressure-composition-temperature (PCT) properties. Other bed design improvements are also presented.

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

    Science.gov (United States)

    Halfen, DeWayne; Ziurys, Lucy M.

    2016-06-01

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

  9. First Principles Studies of Phase Stability and Reaction Dynamics in Complex Metal Hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Chou, Mei-Yin

    2014-09-29

    Complex metal hydrides are believed to be one of the most promising materials for developing hydrogen storage systems that can operate under desirable conditions. At the same time, these are also a class of materials that exhibit intriguing properties. We have used state-of-the-art computational techniques to study the fundamental properties of these materials.

  10. The impact of carbon materials on the hydrogen storage properties of light metal hydrides

    NARCIS (Netherlands)

    Adelhelm, P.A.; de Jongh, P.E.

    2011-01-01

    The safe and efficient storage of hydrogen is still one of the remaining challenges towards fuel cell powered cars. Metal hydrides are a promising class of materials as they allow the storage of large amounts of hydrogen in a small volume at room temperature and low pressures. However, usually the k

  11. Application of thermal electrochemical equation to metal-hydride half-cell system

    Institute of Scientific and Technical Information of China (English)

    LIU Kai-yu; HUANG Bai-yun; ZHANG Ping-min; HE Yue-hui; ZHOU Ke-chao; SU Geng

    2006-01-01

    Application of thermal electrochemical equation to metal-hydride half-cell system was investigated, and the influence of state of charge on the thermal electrochemical performance of hydrogen storage materials was studied. The results show that both the absolute value of the molar enthalpy change and the internal resistance of evolution hydrogen reaction are less than that of absorption hydrogen reaction at the same state of charge. The molar reaction enthalpy change of absorption and evolution of hydride electrode change contrarily with the enhancement of filling degree of hydrogen in hydride electrode. The relation curve of molar reaction enthalpy change to state of charge, both absorption and evolution hydrogen reaction, is close to a constant when the state of charge is 10%-60%, and during state of charge below 10% or state of charge above 60%, the molar reaction enthalpy change varies sharply. Meanwhile, the internal resistance of electrode reaction has an ascending trend with the enhancement on filling degree of hydrogen in hydride electrode in both absorption and evolution hydrogen reaction.

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

    KAUST Repository

    Shaikh Ali, Anaam

    2015-07-06

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Clayton, J C

    1987-10-01

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

  14. 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.

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

    International Nuclear Information System (INIS)

    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

  16. Catalyzed light hydride nanomaterials embedded in a micro-channels hydrogen storage container.

    Science.gov (United States)

    Dehouche, Zahir; Peretti, Hernán A; Yoo, Yeong; Belkacemi, Khaled; Goyette, Jacques

    2009-01-01

    Activated alloys synthesized by arc-melting were examined as catalysts for improving the hydrogen sorption characteristics of nanostructured magnesium hydride, proposed as a reversible hydrogen storage material. The MgH(2)-catalyst absorbing materials were prepared by ball milling of pure MgH(2) with hydrided Zr(47)Ni(53), Zr(9)Ni(11), and other alloys investigated. The nanostructured MgH(2)-intermetallic systems were tested at 250 degrees C and catalyst addition of eutectoid Zr(47)Ni(53) resulted in the fastest desorption time and highest initial desorption rate. The catalyzed Mg-hydride with activated Zr(9)Ni(11) and Zr(7)Ni(10) phases showed fast desorption kinetics. Moreover, the results demonstrated that the composition of dispersed Zr(x)Ni(y)catalysts has a strong influence on the amount of accumulated hydrogen and desorption rate of Mg-nanocomposite. Part two covers advanced micro-channels hydrogen storage module design based on the results of semi-empirical computer simulations of heat and mass transfers in the container. The micro-channels reservoir concept offers many advantages over the conventional metal hydride hydrogen storage system. It is a micro-structured system that can pack a lot of power into a small space and dissipate effectively the heat of the sorption reactions. This review summarizes recent patents related to CNTS.

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

    International Nuclear Information System (INIS)

    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.

  18. Hydride reduction of B-norcholestane 5a,6a-epoxide

    Directory of Open Access Journals (Sweden)

    LJUBINKA B. LORENC

    2002-01-01

    Full Text Available B-Norcholestane epoxide 2 is reduced with lithium aluminium hydride to give either the 3b,6a-diol 3 or the corresponding 3b,5a-diol 4, depending on the quality of the reducing reagent employed. A plausible mechanistic explanation of the obtained results is suggested.

  19. Molecular early main group metal hydrides : synthetic challenge, structures and applications

    NARCIS (Netherlands)

    Harder, Sjoerd

    2012-01-01

    Within the general area of early main group metal chemistry, the controlled synthesis of well-defined metal hydride complexes is a rapidly developing research field. As group 1 and 2 metal complexes are generally highly dynamic and lattice energies for their [MH](infinity) and [MH2](infinity) salts

  20. Reproduction in laboratory of the morphology distribution and orientation of hydrides in different stages fuel cycle; Reproduccion en laboratorio de la morfologia, distribucion y orientacion de hidruros en distintas etapas del ciclo de combustible

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-07-01

    In this paper, the experimental techniques employed to reproduce in the laboratory the distribution, morphology and orientation of the hydrides during the different steps of the nuclear fuel cycle are reported. A cathodic charging technique was employed to produce ZIRLO cladding samples with an homogeneous distribution of hydrides and concentrations of 150, 250, 500, 1200 and 2000 ppm of hydrogen. The treatments developed to produce radial hydride reorientation, hydride blisters and a peripheral rim of hydrides are described.

  1. 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.

  2. 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.

  3. Calculation of thermodynamic hydricities and the design of hydride donors for CO2 reduction

    Science.gov (United States)

    Muckerman, James T.; Achord, Patrick; Creutz, Carol; Polyansky, Dmitry E.; Fujita, Etsuko

    2012-01-01

    We have developed a correlation between experimental and density functional theory-derived results of the hydride-donating power, or “hydricity”, of various ruthenium, rhenium, and organic hydride donors. This approach utilizes the correlation between experimental hydricity values and their corresponding calculated free-energy differences between the hydride donors and their conjugate acceptors in acetonitrile, and leads to an extrapolated value of the absolute free energy of the hydride ion without the necessity to calculate it directly. We then use this correlation to predict, from density functional theory-calculated data, hydricity values of ruthenium and rhenium complexes that incorporate the pbnHH ligand—pbnHH = 1,5-dihydro-2-(2-pyridyl)-benzo[b]-1,5-naphthyridine—to model the function of NADPH. These visible light-generated, photocatalytic complexes produced by disproportionation of a protonated-photoreduced dimer of a metal-pbn complex may be valuable for use in reducing CO2 to fuels such as methanol. The excited-state lifetime of photoexcited [Ru(bpy)2(pbnHH)]2+ is found to be about 70 ns, and this excited state can be reductively quenched by triethylamine or 1,4-diazabicyclo[2.2.2]octane to produce the one-electron-reduced [Ru(bpy)2(pbnHH)]+ species with half-life exceeding 50 μs, thus opening the door to new opportunities for hydride-transfer reactions leading to CO2 reduction by producing a species with much increased hydricity. PMID:22826261

  4. The hydride anion in an extended transition metal oxide array: LaSrCoO3H0.7.

    Science.gov (United States)

    Hayward, M A; Cussen, E J; Claridge, J B; Bieringer, M; Rosseinsky, M J; Kiely, C J; Blundell, S J; Marshall, I M; Pratt, F L

    2002-03-01

    We present the synthesis and structural characterization of a transition metal oxide hydride, LaSrCoO3H0.7, which adopts an unprecedented structure in which oxide chains are bridged by hydride anions to form a two-dimensional extended network. The metal centers are strongly coupled by their bonding with both oxide and hydride ligands to produce magnetic ordering at temperatures up to at least 350 kelvin. The synthetic route is sufficiently general to allow the prediction of a new class of transition metal--containing electronic and magnetic materials. PMID:11884751

  5. Crack growth through the thickness of thin-sheet Hydrided Zircaloy-4

    Science.gov (United States)

    Raynaud, Patrick A. C.

    In recent years, the limits on fuel burnup have been increased to allow an increase in the amount of energy produced by a nuclear fuel assembly thus reducing waste volume and allowing greater capacity factors. As a result, it is paramount to ensure safety after longer reactor exposure times in the case of design-basis accidents, such as reactivity-initiated accidents (RIA). Previously proposed failure criteria do not directly address the particular cladding failure mechanism during a RIA, in which crack initiation in brittle outer-layers is immediately followed by crack growth through the thickness of the thin-wall tubing. In such a case, the fracture toughness of hydrided thin-wall cladding material must be known for the conditions of through-thickness crack growth in order to predict the failure of high-burnup cladding. The fracture toughness of hydrided Zircaloy-4 in the form of thin-sheet has been examined for the condition of through-thickness crack growth as a function of hydride content and distribution at 25°C, 300°C, and 375°C. To achieve this goal, an experimental procedure was developed in which a linear hydride blister formed across the width of a four-point bend specimen was used to inject a sharp crack that was subsequently extended by fatigue pre-cracking. The electrical potential drop method was used to monitor the crack length during fracture toughness testing, thus allowing for correlation of the load-displacement record with the crack length. Elastic-plastic fracture mechanics were used to interpret the experimental test results in terms of fracture toughness, and J-R crack growth resistance curves were generated. Finite element modeling was performed to adapt the classic theories of fracture mechanics applicable to thick-plate specimens to the case of through-thickness crack growth in thin-sheet materials, and to account for non-uniform crack fronts. Finally, the hydride microstructure was characterized in the vicinity of the crack tip by

  6. Hydrophilic pyrazine-based phosphane ligands: synthesis and application in asymmetric hydride transfer and H2-hydrogenation of acetophenone

    NARCIS (Netherlands)

    Nikishkin, N.; Huskens, J.; Verboom, W.

    2013-01-01

    Pyrazine-based hydrophilic phosphanes are useful ligands for the ruthenium- and rhodium-catalyzed hydrogenations of acetophenone under hydride transfer and dihydrogen conditions. The effect of alcohol additives on the catalytic, enantioselective aqueous hydrogenation of acetophenone is examined with

  7. Direct determination of Ge in hot spring waters and coal fly ash samples by hydride generation-ETAAS

    Energy Technology Data Exchange (ETDEWEB)

    Moscoso-Perez, Carmen; Moreda-Pineiro, Jorge; Lopez-Mahia, Purificacion; Muniategui-Lorenzo, Soledad; Fernandez-Fernandez, Esther; Prada-Rodriguez, Dario [Department of Analytical Chemistry, Faculty of Sciences, University of A Coruna, Campus da Zapateira, s/n. E-15071, A Coruna (Spain)

    2004-10-08

    A method for Ge determination in hot spring water and acid extracts from coal fly ash samples involving hydride generation, trapping and atomisation of the hydride generated from Ir-treated graphite tubes (GTs) has been developed. Hydride was generated from hydrochloric acid medium using sodium tetrahydroborate. Several factors affecting the hydride generation, transport, trapping and atomisation efficiency were studied by using a Plackett-Burman design. Results obtained from Plackett-Burman designs suggest that trapping and atomisation temperatures are the significant factors involved on the procedure. The accuracy was studied using NIST-1633a (coal fly ash) reference material. The detection limit of the proposed method was 2.4{mu}gl{sup -1} and the characteristic mass of 233pg was achieved. The Ge concentrations in fly ash and hot spring samples were between 6.25-132{mu}gg{sup -1} and 12.84-36.2{mu}gl{sup -1}.

  8. 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.

  9. An Ion Exchange Study of Possible Hydridized 5f Bonding in theActinides

    Energy Technology Data Exchange (ETDEWEB)

    Diamond, R.M.; Street, Jr., K.; Seaborg, G.T.

    1951-08-28

    A study has been made of the elution behavior of curium(III), americium(III), plutonium(III), actinium(III), plutonium(IV), neptunium(IV), uraniuM(IV), thorium(IV), neptunium(V), plutonium (VI), uranium (VI), lanthanum(III), cerium(III), europium(III), ytterbium(III), ytterium(III), strontium(II), barium(II), radium(II), cesium(I) with 3.2 M, 6.2 M, 9.3 M, and 12.2 M HCl solutions from Dowex-50 cation exchange resin columns. These elutions show that in high concentrations of hydrochloric acid the actinides form complex ions with chloride ion to a much greater extent than the lanthanides. The strengths of the tripositive actinide complex ions apparently go in the order plutonium > americium> curium, although their ionic radii also decrease in this same order. To explain these results, a partial covalent character may be ascribed to the bonding in the transuranium complex ions. It is shown that a reasonable structure for such covalent bonding involves hybridization of the 5f orbitals in the actinide elements.

  10. Effects of Hydride Precipitation on the Stress Developed in ZrO2 Thin Film

    International Nuclear Information System (INIS)

    It has been reported that the effect of thermal redistribution of hydrides across the metal-oxide interface, coupled with thermal feedback on the metal-oxide interface, is a dominating factor in the accelerated oxidation in zirconium alloys cladding PWR fuel. Especially the precipitated and redistributed hydrides are known to relieve the stress imposed onto the metal/oxide interface during the waterside corrosion of zirconium alloys. Without the hydrides the stress exceeds the critical value of 3 GPa which induce the tetragonal ZrO2 phase formation. Therefore, in this study enhanced oxidation due to the precipitated hydrides are experimentally confirmed and stress on the interface is measured with steam beam apparatus in order to support hypothesis hydrides precipitates relieve the stress. In steam beam apparatus, Oxidation reaction occurs only the surface exposed to the steam beam. In order to avoid the oxidation of the other side of specimen, whole chamber is evacuated down to ultra-high vacuum (down to 10-5 Torr). The oxide thickness is measured with weight gain measurement and the curvature of the single side oxidized specimen is measured with spherometer. Specimen is thin film zirconium foil whose thickness is 40μm and diameter is 20mm. Only single surface of specimen exposed to the steam beam oxidizes at 400 .deg. C which is attained by halogen lamp. Basically the measurement technique used in this study is based on the curvature build-up during the single side oxidation process. The stress build-up can be directly evaluated according to the Stoney's formula. Measured stress from the curvature estimation are plotted as a function of thin oxide film thickness. And atmospheric oxidation was also carried out in the electric furnace using the specimen holder, which is designed to protect the other side oxidation of specimen. The stress in the oxide increases as the thickness decreases and the highest stress measured in this study is 5.2 GPa which is higher than

  11. Magnesium based metal hydride reactor incorporating helical coil heat exchanger: Simulation study and optimal design

    International Nuclear Information System (INIS)

    Highlights: • A new 3D modeling for Mg-based metal hydride reactor is proposed. • Hydriding kinetics of Mg-based alloys is modeled based on the experimental data. • Helical coil heat exchanger has better heat transfer effect than traditional one. • The reactor with smaller non-dimensional pitch has favorable performance. - Abstract: Magnesium based metal hydride has been viewed as one of the most commonly-used materials in the practical applications of hydrogen energy systems. The heat and mass transfer processes have significant effects on the hydrogen storage performance of magnesium based metal hydride reactors. Incorporating helical coil heat exchanger into the reactor could be an effective way to improve the performance of heat and mass transfer. In this work, a new three-dimensional model for magnesium based metal hydride reactor with helical coil heat exchanger is proposed and solved using the commercial software package COMSOL Multiphysics V3.5a. The comparison of hydrogen storage behaviors between the reactors incorporating the traditional straight pipe and new helical coil heat exchangers is firstly conducted based on the numerical simulation. The comparison results show that the helical coil heat exchanger has better effect on improving the characteristics of reactor than the straight pipe heat exchanger due to its secondary circulation. The effects of key parameters, including the initial conditions, heat transfer coefficients of heat transfer fluid and helical coil geometry on the characteristics of reactor with the helical coil heat exchanger are also analyzed systematically. It is discovered that larger initial hydrogen pressure and lower initial temperature are beneficial to the improvement of hydrogen absorption kinetics, because of the greater driving force for the hydriding reaction. The results of optimal design suggest that smaller non-dimensional pitch, the ratio of helical pitch to helical diameter, improves the heat and mass transfer

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2003-08-15

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-09-15

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

  14. Structural and mechanical properties of alkali hydrides investigated by the first-principles calculations and principal component analysis

    Science.gov (United States)

    Settouti, Nadera; Aourag, Hafid

    2016-08-01

    The structural and mechanical properties of alkali hydrides (LiH, NaH, KH, RbH, and CsH) were investigated via first-principles calculations which cover the optimized structural parameters. The density functional theory in combination with the generalized gradient approximation (GGA) were used in this study. From the present study, one could note that alkali hydrides are brittle materials and mechanically stable. It was found that stiffness and shear resistance are greater in LiH than in other hydrides. It is more brittle in nature, and comparatively harder than the other materials under study; it also presents a high degree of anisotropy. The results were then investigated and analyzed with principal component analysis (PCA), which is one of the most common techniques in multivariate analysis, was used to explore the correlations among material properties of alkali hydrides and to study their trends. The alkali hydrides obtained by the first-principles calculations were also compared with the alkaline-earth metal hydrides (BeH2, MgH2, CaH2, SrH2, and BaH2) and discussed in this work.

  15. Study of hydride re orientation and mechanical property to evaluate spent fuel integrity during interim Dry storage

    International Nuclear Information System (INIS)

    The operating condition of modern PWRs is getting severer for the nuclear fuel cladding to meet the needs for an economical power generation. As the operating condition, oxide and the subsequent hydrogen caused by the waterside corrosion are generated in the cladding, which decreases the initial ductility of the cladding. Such an oxide and hydrogen act as a negative effect on the cladding safety under the Back End Fuel Cycle. In Korea, 23 nuclear power plants are in operation and lots of spent fuels are on the onsite storage. The onsite storage capacity in Korea is supposed to be full around at the year of 2016 and interim storage facilities could be considered to be constructed before 2016. Therefore, the dry storage concept is becoming a major technical consideration for intermediate spent fuel storage at present. In relation to this, studies on the effects of interim dry storage conditions to spent fuel integrity have recently been initiated in Korea. During the interim dry storage condition, the fuel cladding failure is affected by oxide thickness, hydride content and hydride re-orientation, among that the most important factor of the fuel cladding failure is the hydride reorientation, because the hydride reorientation behavior is shown by decrease cladding temperature in dry storage. however, the hydride reorientation mechanism was not clearly defined. To achieve this, it should be secured that the base technology for integrity assessment in dry storage. In this study, the hydride re orientation and its effect on the mechanical property of fuel cladding was studied

  16. Size Controlled Synthesis of Germanium Nanocrystals: Effect of Ge Precursor and Hydride Reducing Agent

    Directory of Open Access Journals (Sweden)

    Darragh Carolan

    2015-01-01

    Full Text Available Germanium nanocrystals (Ge NCs have attracted increasing attention as a promising alternative to II–VI and IV–VI semiconductor materials as they are cheap, “green,” electrochemically stable, and compatible with existing CMOS processing methods. Germanium is a particularly attractive material for optoelectronic applications as it combines a narrow band gap with high carrier mobilities and a large exciton Bohr radius. Solution-phase synthesis and characterisation of size monodisperse alkyl-terminated Ge NCs are demonstrated. Ge NCs were synthesised under inert atmospheric conditions via the reduction of Ge halide salts (GeX4 by hydride reducing agents within inverse micelles. Regulation of NC size is achieved by variation of germanium precursor and the strength of hydride reducing agents used. UV-Visible absorbance and photoluminescence spectroscopy showed strong significant quantum confinement effects, with moderate absorption in the UV spectral range, and strong emission in the violet with a marked dependence on excitation wavelength.

  17. Technical challenges and future direction for high-efficiency metal hydride thermal energy storage systems

    Science.gov (United States)

    Ward, Patrick A.; Corgnale, Claudio; Teprovich, Joseph A.; Motyka, Theodore; Hardy, Bruce; Sheppard, Drew; Buckley, Craig; Zidan, Ragaiy

    2016-04-01

    Recently, there has been increasing interest in thermal energy storage (TES) systems for concentrated solar power (CSP) plants, which allow for continuous operation when sunlight is unavailable. Thermochemical energy storage materials have the advantage of much higher energy densities than latent or sensible heat materials. Furthermore, thermochemical energy storage systems based on metal hydrides have been gaining great interest for having the advantage of higher energy densities, better reversibility, and high enthalpies. However, in order to achieve higher efficiencies desired of a thermal storage system by the US Department of Energy, the system is required to operate at temperatures >600 °C. Operation at temperatures >600 °C presents challenges including material selection, hydrogen embrittlement and permeation of containment vessels, appropriate selection of heat transfer fluids, and cost. Herein, the technical difficulties and proposed solutions associated with the use of metal hydrides as TES materials in CSP applications are discussed and evaluated.

  18. Aluminum hydride as a hydrogen and energy storage material: Past, present and future

    International Nuclear Information System (INIS)

    Aluminum hydride (AlH3) and its associated compounds make up a fascinating class of materials that have motivated considerable scientific and technological research over the past 50 years. Due primarily to its high energy density, AlH3 has become a promising hydrogen and energy storage material that has been used (or proposed for use) as a rocket fuel, explosive, reducing agent and as a hydrogen source for portable fuel cells. This review covers the past, present and future research on aluminum hydride and includes the latest research developments on the synthesis of α-AlH3 and the other polymorphs (e.g., microcrystallization reaction, batch and continuous methods), crystallographic structures, thermodynamics and kinetics (e.g., as a function of crystallite size, catalysts and surface coatings), high-pressure hydrogenation experiments and possible regeneration routes.

  19. Development of a modular room-temperature hydride storage system for vehicular applications

    Science.gov (United States)

    Capurso, Giovanni; Schiavo, Benedetto; Jepsen, Julian; Lozano, Gustavo; Metz, Oliver; Saccone, Adriana; De Negri, Serena; Bellosta von Colbe, José M.; Klassen, Thomas; Dornheim, Martin

    2016-03-01

    The subject of this paper concerns the development of a vehicular hydrogen tank system, using a commercial interstitial metal hydride as storage material. The design of the tank was intended to feed a fuel cell in a light prototype vehicle, and the chosen hydride material, Hydralloy C5 by GfE, was expected to be able to absorb and desorb hydrogen in a range of pressure suitable for this purpose. A systematic analysis of the material in laboratory scale allows an extrapolation of the thermodynamic and reaction kinetics data. The following development of the modular tank was done according to the requirements of the prototype vehicle propulsion system and led to promising intermediate results. The modular approach granted flexibility in the design, allowing both to reach carefully the design goals and to learn the limiting factors in the sorption process. Proper heat management and suitable equipment remain key factors in order to achieve the best performances.

  20. First-principles investigation of Mg2CoH5 complex hydride

    Institute of Scientific and Technical Information of China (English)

    ZHANG Jian; ZHOU Dian-wu; LIU Jin-shui

    2009-01-01

    Within the framework of density functional theory, crystal structure parameters, physical properties, electronic structures and thermal stability of Mg2CoH5 complex hydride are comprehensively investigated. The optimized structural parameters including lattice constants, atomic positions and bond lengths are well close to the experimental data determined from X-ray and neutron powder diffraction. A detailed study on the energy band, density of states (DOS) and charge density distribution shows the orbital hybridization and bonding characteristics of the complex hydride. It is found that Mg2CoH5 is a semiconductor with a pseudo-gap of about 1.638 1 eV, and there is a mixed ionic-covalent bonding between Co and H in CoH5 complexes embedded in the matrix Mg2+ cations. The calculated formation enthalpy of Mg2CoH5 is in good agreement with the experimentally determined value.

  1. Degradation Behavior of Electrochemical Performance of Sealed-Type Nickel/Metal Hydride Batteries

    Institute of Scientific and Technical Information of China (English)

    李丽; 吴锋; 杨凯

    2003-01-01

    The degradation mechanism of electrochemical performance of sealed-type nickel/metal hydride batteries was investigated. The results indicate that the degradation behavior of Ni/MH battery is not only owing to the lack of electrolyte, but also the deterioration of the active materials on the positive and negative electrodes of Ni/MH batteries. Scanning electron micrographs (SEM), X-ray diffraction (XRD) and laser granularity analyses are presented. The particle pulverization and oxidation during charge/discharge are identified as the main causes for deterioration of the negative and positive electrode in nickel/metal hydride batteries, as well as the cross-section cracking of both anode and cathode.

  2. Recovery Of Electrodic Powder From Spent Nickel-Metal Hydride Batteries (NiMH

    Directory of Open Access Journals (Sweden)

    Shin S.M.

    2015-06-01

    Full Text Available This study was focused on recycling process newly proposed to recover electrodic powder enriched in nickel (Ni and rare earth elements (La and Ce from spent nickel-metal hydride batteries (NiMH. In addition, this new process was designed to prevent explosion of batteries during thermal treatment under inert atmosphere. Spent nickel metal hydride batteries were heated over range of 300°C to 600°C for 2 hours and each component was completely separated inside reactor after experiment. Electrodic powder was successfully recovered from bulk components containing several pieces of metals through sieving operation. The electrodic powder obtained was examined by X-ray diffraction (XRD and energy dispersive X-ray spectroscopy (EDX and image of the powder was taken by scanning electron microscopy (SEM. It was finally found that nickel and rare earth elements were mainly recovered to about 45 wt.% and 12 wt.% in electrodic powder, respectively.

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

    Science.gov (United States)

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

    2016-08-01

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

  4. Electrochemical preconcentration and hydride generation methods for trace determination of selenium by atomic absorption spectrometry

    International Nuclear Information System (INIS)

    The use of atomic absorption spectrometry in combination with two different preconcentration/separation techniques for the determination of trace concentrations of selenium is described. Electrochemical preconcentration onto a platinum electrode with a subsequent atomization of selenium is discussed briefly. Several parameters are considered such as the presence of depolarizers, and the temperature of the electrolyzed solutions. Special attention is payed to the efficiency of the atomization step, and a method to improve this is proposed. Applications of the technique to real samples are also reported. Secondly, the separation of the selenium as the volatile selenium hydride from the sample solution is considered. Several papers in this thesis deal with commonly occurring interferants as nickel and copper and with ways of minimizing or avoiding the interferring effects, whereas other papers relate to more theoretical aspects of the hydride generation process. New methods for the determination of selenium in technical samples with high contents of nickel and copper are also presented

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-11-25

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

  6. Biological impact tests on complex hydrides used as hydrogen storage materials

    Energy Technology Data Exchange (ETDEWEB)

    Tanaka, H.; Kiyobayashi, T.; Kuriyama, N. [Research Institute for Ubiquitous Energy Devices, National Institute of Advanced Industrial Science and Technology (AIST), 1-8-31 Midorigaoka, Ikeda, Osaka 563-8577 (Japan); Tokoyoda, K. [R and D Center, Taiheiyo Cement Corporation, 2-4-2 Osaku, Sakura, Chiba 285-8655 (Japan); Matsumoto, M. [Materials Department, Toyota Central R and D Labs., Inc., Nagakute, Aichi 480-1192 (Japan)

    2010-10-15

    The mutagenicity of a series of the light element hydrides (containing NaAlH{sub 4}, Mg(NH{sub 2}){sub 2}, LiBH{sub 4}, etc.) was examined by evaluating the frequency of mutation in bacterial DNAs. Although some materials were suspected to be slightly mutagenic, their effect was much less malignant than that of well-known potent mutagens. The hydrides exhibited high cytotoxicity, rather than mutagenicity. A Mg(NH{sub 2}){sub 2}-related material was also subjected to a series of toxicity tests on aqueous organisms, i.e., algae, water fleas and fish. The result suggests that the material is as toxic as alkaline metal hydroxides, such as NaOH and KOH. (author)

  7. Use of Solid Hydride Fuel for Improved long-Life LWR Core Designs

    Energy Technology Data Exchange (ETDEWEB)

    Greenspan, E

    2006-04-30

    The primary objective of this project was to assess the feasibility of improving the performance of PWR and BWR cores by using solid hydride fuels instead of the commonly used oxide fuel. The primary measure of performance considered is the bus-bar cost of electricity (COE). Additional performance measures considered are safety, fuel bundle design simplicity – in particular for BWR’s, and plutonium incineration capability. It was found that hydride fuel can safely operate in PWR’s and BWR’s without restricting the linear heat generation rate of these reactors relative to that attainable with oxide fuel. A couple of promising applications of hydride fuel in PWR’s and BWR’s were identified: (1) Eliminating dedicated water moderator volumes in BWR cores thus enabling to significantly increase the cooled fuel rods surface area as well as the coolant flow cross section area in a given volume fuel bundle while significantly reducing the heterogeneity of BWR fuel bundles thus achieving flatter pin-by-pin power distribution. The net result is a possibility to significantly increase the core power density – on the order of 30% and, possibly, more, while greatly simplifying the fuel bundle design. Implementation of the above modifications is, though, not straightforward; it requires a design of completely different control system that could probably be implemented only in newly designed plants. It also requires increasing the coolant pressure drop across the core. (2) Recycling plutonium in PWR’s more effectively than is possible with oxide fuel by virtue of a couple of unique features of hydride fuel – reduced inventory of U-238 and increased inventory of hydrogen. As a result, the hydride fuelled core achieves nearly double the average discharge burnup and the fraction of the loaded Pu it incinerates in one pass is double that of the MOX fuel. The fissile fraction of the Pu in the discharged hydride fuel is only ~2/3 that of the MOX fuel and the

  8. Thermal and mechanical properties of hydrides of Zr–Hf alloys

    International Nuclear Information System (INIS)

    Polycrystalline bulk samples of δ-phase Hf hydrides with various Zr contents were prepared and their high-temperature stability and thermal and mechanical properties were investigated. The phase structure was examined between room temperature and 973 K using high-temperature X-ray diffraction and thermogravimetric–differential thermal analysis. From room temperature to 673 K, the coefficient of linear thermal expansion, specific heat capacity, and thermal conductivity were evaluated. The Vickers hardness and sound velocity were measured at room temperature, and the elastic modulus was evaluated. The effect of the Zr content on the high-temperature stability and the thermal and mechanical properties of Hf hydrides was studied. (author)

  9. A twist on facial selectivity of hydride reductions of cyclic ketones: twist-boat conformers in cyclohexanone, piperidone, and tropinone reactions.

    Science.gov (United States)

    Neufeldt, Sharon R; Jiménez-Osés, Gonzalo; Comins, Daniel L; Houk, K N

    2014-12-01

    The role of twist-boat conformers of cyclohexanones in hydride reductions was explored. The hydride reductions of a cis-2,6-disubstituted N-acylpiperidone, an N-acyltropinone, and tert-butylcyclohexanone by lithium aluminum hydride and by a bulky borohydride reagent were investigated computationally and compared to experiment. Our results indicate that in certain cases, factors such as substrate conformation, nucleophile bulkiness, and remote steric features can affect stereoselectivity in ways that are difficult to predict by the general Felkin-Anh model. In particular, we have calculated that a twist-boat conformation is relevant to the reactivity and facial selectivity of hydride reduction of cis-2,6-disubstituted N-acylpiperidones with a small hydride reagent (LiAlH4) but not with a bulky hydride (lithium triisopropylborohydride).

  10. Bulk and surface energetics of crystalline lithium hydride: Benchmarks from quantum Monte Carlo and quantum chemistry

    OpenAIRE

    Binnie, S. J.; Nolan, S. J.; Drummond, Neil; Alfe`, D.; Allan, N. L; Manby, F. R.; Gillan, M. J.

    2010-01-01

    We show how accurate benchmark values of the surface formation energy of crystalline lithium hydride can be computed by the complementary techniques of quantum Monte Carlo (QMC) and wavefunction-based molecular quantum chemistry. To demonstrate the high accuracy of the QMC techniques, we present a detailed study of the energetics of the bulk LiH crystal, using both pseudopotential and all-electron approaches. We show that the equilibrium lattice parameter agrees with experiment to within 0.03...

  11. Develop improved metal hydride technology for the storage of hydrogen. Final technical report

    Energy Technology Data Exchange (ETDEWEB)

    Sapru, K.

    1998-12-04

    The overall objective was to develop commercially viable metal hydrides capable of reversibly storing at least 3 wt.% hydrogen for use with PEM fuel cells and hydrogen fueled internal combustion engine (HICE) applications. Such alloys are expected to result in system capacities of greater than 2 wt.%, making metal hydride storage systems (MHSS`s) a practical means of supplying hydrogen for many consumer applications. ECD`s (Energy Conversion Devices, Inc.) past work on sputtered thin films of transition metal-based alloys led to the commercialization of it`s nickel/metal hydride batteries, and similar work on thin film Mg-based alloys demonstrated potential to achieve very high gravimetric and volumetric energy densities approaching 2,500 Wh/Kg and 2,500 Wh/M{sup 3} respectively. Under this 2-year cost shared project with the DOE, the authors have successfully demonstrated the feasibility of scaling up the Mg-based hydrides from thin film to bulk production without substantial loss of storage capacity. ECD made progress in alloy development by means of compositional and process modification. Processes used include Mechanical Alloying, Melt spinning and novel Gas Phase Condensation. It was showed that the same composition when prepared by melt-spinning resulted in a more homogeneous material having a higher PCT plateau pressure as compared to mechanical alloying. It was also shown that mechanically alloyed Mg-Al-Zn results in much higher plateau pressures, which is an important step towards reducing the desorption temperature. While significant progress has been made during the past two years in alloy development and understanding the relationship between composition, structure, morphology, and processing parameters, additional R and D needs to be performed to achieve the goals of this work.

  12. The Cracking Induced by Oxidation-Hydriding in Welding Joints of Zircaloy-4 Plates

    Institute of Scientific and Technical Information of China (English)

    周邦新; 姚美意; 苗志; 李强; 刘文庆

    2003-01-01

    The welding joints of Zircaloy-4 plates obtained by diffusion welding at 800℃ under pressure in vacuum were cracked during autoclave tests at 400℃ superheated steam after exposure longer than 150 days. The section of specimens was examined by optical microscopy and the composition at the tips of cracking was analyzed by electron microprobe. The result shows that the combination of oxidation and hydriding induced cracking is responsible for this failure of the welding joints.

  13. The challenge of storage in the hydrogen energy cycle: nanostructured hydrides as a potential solution

    OpenAIRE

    Hanlon, James M.; Reardon, Hazel; Tapia-Ruiz, Nuria; Gregory, Duncan H.

    2012-01-01

    Hydrogen has the capacity to provide society with the means to carry ‘green’ energy between the point of generation and the point of use. A sustainable energy society in which a hydrogen economy predominates will require renewable generation provided, for example, by artificial photosynthesis and clean, efficient energy conversion effected, for example, by hydrogen fuel cells. Vital in the hydrogen cycle is the ability to store hydrogen safely and effectively. Solid-state storage in hydrides ...

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

    Science.gov (United States)

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

    2013-11-01

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

  15. Preparation and Properties of Zirconium Hydride on the Surface of MCM-41 Mesoporous Molecular Sieves

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Zirconium monohydride bonded to the framework oxygen of MCM-41 surface was prepared by the reaction of tetraneopentyl zirconium with MCM-41 surface hydroxyl groups, followed by the hydrogenolysis of the resulted product. The surface hydride was characterized by using infrared spectroscopy, solid-state NMR, elemental analysis, gas-phase chromatography and chemical probing reaction. It was shown that this surface species is stable below 150 ℃ and can catalytically crack alkanes into methane and ethane at 100 ℃.

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

    OpenAIRE

    Millet, P.; C. Decaux; R. Ngameni; Guymont, M.

    2007-01-01

    Analysis of phase transformation processes observed in hydrogen absorbing materials (pure metals, alloys, or compounds) is still a matter of active research. Using pneumato-chemical impedance spectroscopy (PIS), it is now possible to analyze the mechanism of hydriding reactions induced by the gas phase. Experimental impedance diagrams, measured on activated LaNi5 in single- and two-phase domains, are reported in this paper. It is shown that their shape is mostly affected by the slope of the i...

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

    Science.gov (United States)

    Jokisaari, Andrea M.

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

  18. Topotactic Solid-State Metal Hydride Reductions of Sr2MnO4.

    Science.gov (United States)

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

    2015-05-01

    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. PMID:25894860

  19. Thermal creep of hydride Zircaloy-4 plates under dry storage conditions

    International Nuclear Information System (INIS)

    Dry storage is one of the most realistic options for interim storage until fuel reprocessing or final disposal. During dry storage, the fuel cladding temperature rises up around 400 .deg. C due to poor heat conductivity of inert gases surrounding the cladding tubes as compared to water in wet storage. Under these conditions, creep and hydride effects are important degradation mechanisms for spent nuclear fuel cladding. However, in Korea, there are few experimental results on not only in-pile but also out-of-pile spent nuclear fuel cladding to understand degradation mechanisms and to determine the domestic safety criteria. Plate creep tests were carried out up to rupture on Zircaloy-4 tensile specimen under the stresses 140 MPa and 160 MPa at 400 .deg. C. The results obtained were as follows: (1) The more stress applied, the shorter creep rupture time was and the smaller secondary creep rates were. (2) Secondary creep rates of hydride specimens were higher than those of as-received specimens. (3) Creep rupture time of hydride specimens was shorter than that of as-received specimens

  20. Hydriding and Dehydriding Characteristics of Mechanically Alloyed LaMg17Ni Composite Material

    Institute of Scientific and Technical Information of China (English)

    李谦; 蒋利军; 林勤; 周国治; 詹峰; 郑强; 魏秀英

    2003-01-01

    A composite material with the nominal composition LaMg17Ni was synthesized by mechanical alloying and the hydriding/dehydriding (H/D) behaviors of this material were studied at several temperatures. This material has a hydrogen storage capacity (5.76% H2, mass fraction) lower than conventionally alloyed La2Mg17 (6.63% H2, mass fraction) without activation but shows a superior hydriding/dehydriding kinetic property. At 523 K it absorbed 4.97% (mass fraction) in less than 1 min, approximately 100 times faster than La2Mg17 alloy under the same conditions. This attractive kinetic property of the alloy can be ascribed to the catalytic action of Mg2Ni, LaH2 and La as well as the multiphase structure formed in the preparation processes. The relationships between the equilibrium plateau pressure and the temperature can be expressed as lgpeq=-2797/T+4.267 (553 K≤T≤623 K) for hydriding and lgpeq=-3957/T+6.063(553 K≤T≤623 K) for dehydriding.

  1. Insertion and isomerisation of internal olefins at alkylaluminium hydride: catalysis with zirconocene dichloride.

    Science.gov (United States)

    Weliange, Nandita M; McGuinness, David S; Gardiner, Michael G; Patel, Jim

    2015-12-14

    The insertion of internal olefins (hydroalumination) and chain walking isomerisation at di-n-octylaluminium hydride [Al(Oct)2H], promoted by zirconocene dichloride [Cp2ZrCl2] has been studied. The reaction between [Cp2ZrCl2] and [Al(Oct)2H] in non-polar solvents leads to clusters containing bridging hydride ligands between Zr and Al. This system promotes hydroalumination of 1-octene but is largely ineffective for internal octenes (2-, 3-, 4-octene). In tetrahydrofuran the Zr-Al hydride clusters formed are more reactive and catalyse insertion and isomerisation of internal olefins to primary metal-alkyls, although this is accompanied by catalyst deactivation. Elimination and removal of 1-octene from the system post insertion/isomerisation was attempted, but it was found that the presence of the Zr catalyst leads to back-isomerisation to internal octenes, along with further decomposition with n-octane formation. Some possible pathways of catalyst decomposition, involving reduction of Zr and alkane elimination, have been studied theoretically. PMID:26530377

  2. The Separation of Hydrogen Tritium and Tritium Hydride by Gas Chromatography

    International Nuclear Information System (INIS)

    Now that successful separation of hydrogen, deuterium and hydrogen deuteride has been achieved by gas chromatography, similar studies are being made dealing with mixtures of hydrogen, tritium and tritium hydride. Since tritium is used in tracer quantities the usual katharometer cannot be employed for its detection. This difficulty has been overcome by providing immediately following the katharometer a vibrating reed electrometer equipped with a high resistance leak which allows continuous monitoring of the activity of any tritium or tritium hydride emerging from the column by means of synchronized recorders. Separation of such mixtures has been tested with columns packed with palladium on silica, silica, alumina, and alumina coated with chromium oxide or ferric oxide. No effective separation was obtained with the palladium on silica column. Good separation was achieved with the plain silica column where hydrogen was employed as the carrier gas, but helium failed to elute the isotopes. Satisfactory results were obtained with the coated, partially deactivated alumina packing when helium or neon was the carrier gas, but the best separation was found with a column packing of uncoated activated alumina. Calibration with helium-tritium mixtures of known activity plus equilibrated hydrogen-tritium mixtures also of known activity allows quantitative estimation of tritium and tritium hydride. (author)

  3. Mononuclear Phenolate Diamine Zinc Hydride Complexes and Their Reactions With CO2.

    Science.gov (United States)

    Brown, Neil J; Harris, Jonathon E; Yin, Xinning; Silverwood, Ian; White, Andrew J P; Kazarian, Sergei G; Hellgardt, Klaus; Shaffer, Milo S P; Williams, Charlotte K

    2014-03-10

    The synthesis, characterization, and zinc coordination chemistry of the three proligands 2-tert-butyl-4-[tert-butyl (1)/methoxy (2)/nitro (3)]-6-{[(2'-dimethylaminoethyl)methylamino]methyl}phenol are described. Each of the ligands was reacted with diethylzinc to yield zinc ethyl complexes 4-6; these complexes were subsequently reacted with phenylsilanol to yield zinc siloxide complexes 7-9. Finally, the zinc siloxide complexes were reacted with phenylsilane to produce the three new zinc hydride complexes 10-12. The new complexes 4-12 have been fully characterized by NMR spectroscopy, mass spectrometry, and elemental analyses. The structures of the zinc hydride complexes have been probed using VT-NMR spectroscopy and X-ray diffraction experiments. These data indicate that the complexes exhibit mononuclear structures at 298 K, both in the solid state and in solution (d 8-toluene). At 203 K, the NMR signals broaden, consistent with an equilibrium between the mononuclear and dinuclear bis(μ-hydrido) complexes. All three zinc hydride complexes react rapidly and quantitatively with carbon dioxide, at 298 K and 1 bar of pressure over 20 min, to form the new zinc formate complexes 13-15. The zinc formate complexes have been analyzed by NMR spectroscopy and VT-NMR studies, which reveal a temperature-dependent monomer-dimer equilibrium that is dominated by the mononuclear species at 298 K. PMID:24882918

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

    International Nuclear Information System (INIS)

    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

  5. The role of chemical free energy and elastic strain in the nucleation of zirconium hydride

    Energy Technology Data Exchange (ETDEWEB)

    Barrow, A.T.W. [Nuclear Materials Group, Department of Mechanical and Materials Engineering, Queen’s University, Kingston, Ontario K7L 3N6 (Canada); Toffolon-Masclet, C. [CEA-Saclay, Nuclear Materials Department, SRMA/LA2M, F-91191 Gif-Sur-Yvette (France); Almer, J. [Argonne National Laboratory, Argonne, IL 60439 (United States); Daymond, M.R., E-mail: daymond@me.queensu.ca [Nuclear Materials Group, Department of Mechanical and Materials Engineering, Queen’s University, Kingston, Ontario K7L 3N6 (Canada)

    2013-10-15

    In this work a combination of synchrotron X-ray diffraction and thermodynamic modelling has been used to study the dissolution and precipitation of zirconium hydride in α-Zr establishing the role of elastic misfit strain and chemical free energy in the α → α + δ phase transformation. The nucleation of zirconium hydride is dominated by the chemical free energy where the chemical driving force for hydride precipitation is proportional to the terminal-solid solubility for precipitation and can be predicted by a function that is analogous to the universal nucleation parameter for the bainite transformation in ferrous alloys. The terminal-solid solubility for precipitation was found to be kinetically limited ⩾287 °C at a cooling rate of 5 °C min{sup −1} or greater. The terminal solubilities were established using an offset method applied to the lattice strain data where a resolution of ∼10 wppm H can be achieved in the 〈c〉-direction. This is aided by the introduction of intra-granular strains in the 〈c〉-direction during cooling as a result of the thermal expansion anisotropy which increases the anisotropy associated with the misfitting H atoms within the α-Zr lattice.

  6. Superconductivity of novel tin hydrides (Sn(n)H(m)) under pressure.

    Science.gov (United States)

    Mahdi Davari Esfahani, M; Wang, Zhenhai; Oganov, Artem R; Dong, Huafeng; Zhu, Qiang; Wang, Shengnan; Rakitin, Maksim S; Zhou, Xiang-Feng

    2016-01-01

    With the motivation of discovering high-temperature superconductors, evolutionary algorithm USPEX is employed to search for all stable compounds in the Sn-H system. In addition to the traditional SnH4, new hydrides SnH8, SnH12 and SnH14 are found to be thermodynamically stable at high pressure. Dynamical stability and superconductivity of tin hydrides are systematically investigated. I4m2-SnH8, C2/m-SnH12 and C2/m-SnH14 exhibit higher superconducting transition temperatures of 81, 93 and 97 K compared to the traditional compound SnH4 with Tc of 52 K at 200 GPa. An interesting bent H3-group in I4m2-SnH8 and novel linear H in C2/m-SnH12 are observed. All the new tin hydrides remain metallic over their predicted range of stability. The intermediate-frequency wagging and bending vibrations have more contribution to electron-phonon coupling parameter than high-frequency stretching vibrations of H2 and H3. PMID:26964636

  7. Nanometer-scale hydrogen 'portals' for the control of magnesium hydride formation.

    Science.gov (United States)

    Chung, Chia-Jung; Nivargi, Chinmay; Clemens, Bruce

    2015-11-21

    Magnesium and Mg-based material systems are attractive candidates for hydrogen storage but limited by unsuitable thermodynamic and kinetic properties. In particular, the kinetics are too slow at room temperature and atmospheric pressure. To study the hydride formation kinetics in a controlled way, we have designed a unique 'nanoportal' structure of Pd nanoparticles deposited on epitaxial Mg thin films, through which the hydride will nucleate only under Pd nanoparticles. We propose a growth mechanism for the hydrogenation reaction in the nanoportal structure, which is supported by scanning electron microscopy (SEM) images of hydrogenated samples exhibiting consistent results. Interestingly, the grain boundaries of Mg films play an important role in hydride nucleation and growth processes. Kinetic modeling based on the Johnson-Mehl-Avrami-Kolmogorov (JMAK) formalism seems to agree with the two-dimensional nucleation and growth mechanism hypothesized and the overall reaction rate is limited by hydrogen flux through the interface between the Pd nanoparticle and the underlying Mg film. The fact that in our structure Mg can be transformed completely into MgH2 with only a small percentage of Pd nanoparticles offers possibilities for future on-board storage applications. PMID:26455282

  8. 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.

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

    Science.gov (United States)

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

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

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

    Institute of Scientific and Technical Information of China (English)

    Thananchai Leephakpreeda

    2012-01-01

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

  11. Rapid Microwave Synthesis, Characterization and Reactivity of Lithium Nitride Hydride, Li4NH

    Directory of Open Access Journals (Sweden)

    Nuria Tapia-Ruiz

    2013-11-01

    Full Text Available Lithium nitride hydride, Li4NH, was synthesised from lithium nitride and lithium hydride over minute timescales, using microwave synthesis methods in the solid state for the first time. The structure of the microwave-synthesised powders was confirmed by powder X-ray diffraction [tetragonal space group I41/a; a = 4.8864(1 Å, c = 9.9183(2 Å] and the nitride hydride reacts with moist air under ambient conditions to produce lithium hydroxide and subsequently lithium carbonate. Li4NH undergoes no dehydrogenation or decomposition [under Ar(g] below 773 K. A tetragonal–cubic phase transition, however, occurs for the compound at ca. 770 K. The new high temperature (HT phase adopts an anti-fluorite structure (space group Fm 3̅ m; a = 4.9462(3 Å with N3− and H− ions disordered on the 4a sites. Thermal treatment of Li4NH under nitrogen yields a stoichiometric mixture of lithium nitride and lithium imide (Li3N and Li2NH respectively.

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

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

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

  13. Microstructure and hydride embrittlement of zirconium model alloys containing niobium and tin

    International Nuclear Information System (INIS)

    Research highlights: → Addition of Nb and Sn delayed recrystallization during final annealing treatment. → Sn was more effective in modifying hydride morphology and alignment. → Both Nb and Sn strengthened Zr alloys, where Sn was more effective. → Degree of ductility loss with hydrogen depended on Nb and Sn contents. - Abstract: To investigate the effects of the addition of Nb and Sn to Zr alloys on hydride embrittlement, experimental alloys with different Nb and Sn contents were prepared and charged with hydrogen up to 850 ppm. When Nb and Sn were added, recrystallization was delayed in Zr alloys, mainly due to β-Nb precipitates in Nb containing alloys and Sn solute atoms in Sn containing alloys, respectively. Among the two alloying elements, Sn was more effective in delaying recrystallization. Tensile test results showed that both Nb and Sn strengthened the Zr alloys, and tensile strengths were nearly independent of the absorbed hydrogen content. While resistance to hydride embrittlement was significantly improved with Nb addition to Zr alloys due to increased hydrogen solubility and delayed recrystallization, no effect of Sn addition was observed.

  14. Equation of state of palladium hydride and deuteride to 100 GPa

    Science.gov (United States)

    Brownsberger, Keenan; Ahart, Muhtar; Somayazulu, Maddury; Gramsch, Stephen; Hemley, Russell

    To study the behavior of palladium hydrides under pressure, we loaded palladium foils in hydrogen or deuterium environments in two separate diamond anvil cells. We subsequently measured x-ray diffraction up to 100 GPa at room temperature. No structural phase transition was observed for either PdDx or PdHx between 0 GPa and 100 GPa. The pressure-volume data were fitted with the third-order Birch-Murnaghan equation of state, which gave an initial volume of 10.8 cm3/mol, a bulk modulus of 153 GPa, and its derivative of 4.3 for palladium hydride. An initial volume of 10.6 cm3/mol, a bulk modulus of 162 GPa, and its pressure derivative of 4.6 were determined for palladium deuteride. From initial volumes, we conclude that x =1 for both PdDx and PdHx. This work is supported by the Carnegie-DOE Alliance Center. EOS of palladium hydride and deuteride to 100 GPa.

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

    Science.gov (United States)

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

    2012-03-19

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

  16. 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.

  17. Theoretical study of a novel solar trigeneration system based on metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Meng, Xiangyu; Yang, Fusheng; Bao, Zewei; Deng, Jianqiang; Serge, Nyallang N.; Zhang, Zaoxiao [State Key Laboratory of Multiphase Flow in Power Engineering, Xi' an Jiaotong University, Xi' an 710049 (China)

    2010-06-15

    In order to utilize the low grade heat energy efficiently, the preliminary scheme of a metal hydride based Combined Cooling, Heating and Power (CCHP) system driven by solar energy and industrial waste heat was proposed, in which both refrigeration and power generation are achieved. Following a step-by-step procedure recently developed by the authors, two pairs of metal hydrides were selected for the CCHP system. The working principle of the system was discussed in detail and further design of the configuration for CCHP was conducted. Based on the cycle mentioned above, the models of energy conversion and exergy analysis were set up. The multi-element valued method was used to assess the performance of the CCHP system in a whole sense, thus the analysis of influence factors on the system performance can be carried out. The typical climate conditions of Xi'an in 2005 were taken for discussion, and the results showed that the system performance is mainly affected by the quantity of solar radiation energy. The objective of the system's optimization is to increase the exergy efficiency of the metal hydride heat pump, based on the quantity of solar radiation energy. The comparison with two different traditional types of CCHP systems proved that the novel CCHP system is superior to the traditional CCHP systems concerning the integrated performance. (author)

  18. Hydride-catalyzed corrosion of plutonium by air: Initiation by plutonium monoxide monohydride

    International Nuclear Information System (INIS)

    Chemistry and kinetics of air reactions with plutonium monoxide monohydride (PuOH) and with mixtures of the oxide hydride and plutonium metal are defined by results of pressure-volume-temperature (PVT) measurements. Test with specimens prepared by total and partial corrosion of plutonium in 0.05 M sodium chloride solution show that reaction of residual water continues to generate H2 after liquid water is removed by evacuation. Rapid exposure of PuOH to air at room temperature does not produce a detectable reaction, but similar exposure of a partially corroded metal sample containing Pu and PuOH results in hydride (PuHx)-catalyzed corrosion of the residual Pu. Kinetics of he first-order reaction resulting in formation of the PuHx catalyst and of the indiscriminate reaction of N2 and O2 with plutonium metal are defined. The rate of the catalyzed Pu+air reaction is independent of temperature (Ea = 0), varies as the square of air pressure, and equals 0.78 ± 0.03 g Pu/cm2 min in air at one atmosphere. The absence of pyrophoric behavior for PuOH and differences in the reactivities of PuOH and PuOH + Pu mixtures are attributed to kinetic control by gaseous reaction products. Thermodynamic properties of the oxide hydride are estimated, particle size distributions of corrosion products are presented, and potential hazards associated with products formed by aqueous corrosion of plutonium are discussed

  19. Empirical and physics based mathematical models of uranium hydride decomposition kinetics with quantified uncertainties.

    Energy Technology Data Exchange (ETDEWEB)

    Salloum, Maher N.; Gharagozloo, Patricia E.

    2013-10-01

    Metal particle beds have recently become a major technique for hydrogen storage. In order to extract hydrogen from such beds, it is crucial to understand the decomposition kinetics of the metal hydride. We are interested in obtaining a a better understanding of the uranium hydride (UH3) decomposition kinetics. We first developed an empirical model by fitting data compiled from different experimental studies in the literature and quantified the uncertainty resulting from the scattered data. We found that the decomposition time range predicted by the obtained kinetics was in a good agreement with published experimental results. Secondly, we developed a physics based mathematical model to simulate the rate of hydrogen diffusion in a hydride particle during the decomposition. We used this model to simulate the decomposition of the particles for temperatures ranging from 300K to 1000K while propagating parametric uncertainty and evaluated the kinetics from the results. We compared the kinetics parameters derived from the empirical and physics based models and found that the uncertainty in the kinetics predicted by the physics based model covers the scattered experimental data. Finally, we used the physics-based kinetics parameters to simulate the effects of boundary resistances and powder morphological changes during decomposition in a continuum level model. We found that the species change within the bed occurring during the decomposition accelerates the hydrogen flow by increasing the bed permeability, while the pressure buildup and the thermal barrier forming at the wall significantly impede the hydrogen extraction.

  20. Metal hydride work pair development and its application on automobile air conditioning systems

    Institute of Scientific and Technical Information of China (English)

    QIN Feng; CHEN Jiang-ping; ZHANG Wen-feng; CHEN Zhi-jiu

    2007-01-01

    Aiming at developing exhaust gas driving automobile air conditioning systems, a hydride pair LaNi4.61Mn0.26A10.13/La0.6Y0.4Ni4.8Mn0.2 was developed working at 393~473 K/293~323 K/263~273 K. Property tests showed that both alloys have flat plateau slopes and small hystereses; system theoretical coefficient of performance (COP) is 0.711. Based on this work pair, a function proving automobile metal hydride refrigeration system was constructed. The equivalent thermal conductivities of the activated reaction beds were merely 1.1~1.6 W/(m·K), which had not met practical requirement. Intermittent refrigeration cycles were achieved and the average cooling power was 84.6 W at 423 K/303 K/273 K with COP being 0.26. By altering cycling parameters, experiment data showed that cooling power and system COP increase with the growth of heat source temperature as well as pre-heating and regeneration time while decrease with heat sink temperature increment. This study confirms the feasibility of automobile metal hydride refrigeration systems, while heat transfer properties of reaction beds still need to be improved for better performance.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-07-14

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

  2. Identification of the zirconium hydrides metallography in zircaloy-2; Contribucion al estudio por metalografia de los hidruros de circonio en Zircaloy-2

    Energy Technology Data Exchange (ETDEWEB)

    Garcia Gonzalez, F.

    1968-07-01

    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.

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

    KAUST Repository

    Mazoyer, Etienne

    2011-12-02

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

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

    Science.gov (United States)

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

    2008-03-01

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

  5. Bio-inspired transition metal-organic hydride conjugates for catalysis of transfer hydrogenation: experiment and theory.

    Science.gov (United States)

    McSkimming, Alex; Chan, Bun; Bhadbhade, Mohan M; Ball, Graham E; Colbran, Stephen B

    2015-02-01

    Taking inspiration from yeast alcohol dehydrogenase (yADH), a benzimidazolium (BI(+) ) organic hydride-acceptor domain has been coupled with a 1,10-phenanthroline (phen) metal-binding domain to afford a novel multifunctional ligand (L(BI+) ) with hydride-carrier capacity (L(BI+) +H(-) ⇌L(BI) H). Complexes of the type [Cp*M(L(BI) )Cl][PF6 ]2 (M=Rh, Ir) have been made and fully characterised by cyclic voltammetry, UV/Vis spectroelectrochemistry, and, for the Ir(III) congener, X-ray crystallography. [Cp*Rh(L(BI) )Cl][PF6 ]2 catalyses the transfer hydrogenation of imines by formate ion in very goods yield under conditions where the corresponding [Cp*Ir(L(BI) )Cl][PF6 ] and [Cp*M(phen)Cl][PF6 ] (M=Rh, Ir) complexes are almost inert as catalysts. Possible alternatives for the catalysis pathway are canvassed, and the free energies of intermediates and transition states determined by DFT calculations. The DFT study supports a mechanism involving formate-driven RhH formation (90 kJ mol(-1) free-energy barrier), transfer of hydride between the Rh and BI(+) centres to generate a tethered benzimidazoline (BIH) hydride donor, binding of imine substrate at Rh, back-transfer of hydride from the BIH organic hydride donor to the Rh-activated imine substrate (89 kJ mol(-1) barrier), and exergonic protonation of the metal-bound amide by formic acid with release of amine product to close the catalytic cycle. Parallels with the mechanism of biological hydride transfer in yADH are discussed.

  6. Microstructural studies and crystallographic orientation of different zones and δ-hydrides in resistance welded Zircaloy-4 sheets

    Science.gov (United States)

    Kiran Kumar, N. A. P.; Szpunar, Jerzy. A.; He, Zhang

    2011-07-01

    The cold worked stress relieved (CWSR) Zircaloy-4 sheet used as endplate in nuclear fuel bundle is resistance welded with an endcap in argon environment. Later the welded sample is hydrided in a gaseous atmosphere at 400 °C. Optical microscopy (OM), electron backscatter diffraction (EBSD) and X-ray diffraction (XRD) were used to examine the morphology and crystal orientation of the hydrides. The microstructural changes in different areas of the weld zone, heat affected zone (HAZ) and the as-received zone were analyzed using EBSD technique. Optical examination showed complete random morphological orientation of hydrides and predominantly basket-weave structure in the weld zone, with very few colonies of parallel plate structures. Variant selection for α-phase formation inside prior β-grains was identified at the weld centre. As we move from the weld centre to the as-received zone, the variant selection is found to be less probable. The δ-hydride platelets at the weld zone were always found to be growing perpendicular to the α-colonies having angular difference of 60-63° and follow (0 0 0 1) α-Zr//{1 1 1}δ-ZrH 1.5 orientation relationship with the zirconium matrix. Proposed description of complex distribution of hydrides and alloy microstructure at the weld and heat affected zone will contribute to a better understanding of mechanisms of failure of fuel cladding in various types of nuclear reactors.

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

    Institute of Scientific and Technical Information of China (English)

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

    2012-01-01

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

  8. Effect of Chloride ion and Zirconium hydride on thr corrosion and SCC behaviors of functionally graded Zirconium alloy p.683

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Y. [Department of Metallurgical and Materials Engineering, Sunmoon University, Asam (Korea, Republic of); Kim, B. G.; Lee, J. W.; Kang, Y. H. [Korea Atomic Energy Research Institute, Taejon (Korea, Republic of)

    2000-07-01

    Effect of chloride ion and zirconium hydride on the corrosion and stress corrosion cracking behaviors of functionally graded zirconium alloy was studied to develop an advanced nuclear cladding tubing. The functionally graded zirconium alloy had composition gradient of niobium, which was prepared with a hot pressing followed by cold deformation. The corrosion rates and potentials decreased with increasing FeCl{sub 3} and hydride content. The corrosion potentials before and after hydriding are -4.3 V{sub SHE}, 8.8x10{sup -5} A{sub cm}{sup -2} and -12.5 V{sub SHE}, 3.9x10{sup -4} A{sub cm}{sup -2}, respectively. The stress corrosion cracking susceptibility decreased with elongation rate, indicating the saturation value at 5x10{sup -7} sec{sup -1}. SEM observation showed that brittle fracture with corrosion products and pits were observed on the failed surface of hydrided zirconium alloy, suggesting anodic dissolution occurred during exposure after cracking growth along zirconium hydrides. (author)

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

    Institute of Scientific and Technical Information of China (English)

    LI Song-lin(李松林); R.A.Varin

    2004-01-01

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

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

    Science.gov (United States)

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

    2016-09-01

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

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

    Science.gov (United States)

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

    2016-09-14

    Carbon-carbon bond cleavage of benzene by transition metals is of great fundamental interest and practical importance, as this transformation is involved in the production of fuels and other important chemicals in the industrial hydrocracking of naphtha on solid catalysts. Although this transformation is thought to rely on cooperation of multiple metal sites, molecular-level information on the reaction mechanism has remained scarce to date. Here, we report the DFT studies of the ring cleavage and contraction of benzene by a molecular trinuclear titanium hydride cluster. Our studies suggest that the reaction is initiated by benzene coordination, followed by H2 release, C6H6 hydrometalation, repeated C-C and C-H bond cleavage and formation to give a MeC5H4 unit, and insertion of a Ti atom into the MeC5H4 unit with release of H2 to give a metallacycle product. The C-C bond cleavage and ring contraction of toluene can also occur in a similar fashion, though some details are different due to the presence of the methyl substituent. Obviously, the facile release of H2 from the metal hydride cluster to provide electrons and to alter the charge population at the metal centers, in combination with the flexible metal-hydride connections and dynamic redox behavior of the trimetallic framework, has enabled this unusual transformation to occur. This work has not only provided unprecedented insights into the activation and transformation of benzene over a multimetallic framework but it may also offer help in the design of new molecular catalysts for the activation and transformation of inactive aromatics. PMID:27549745

  12. A copper(I) homocubane collapses to a tetracapped tetrahedron upon hydride insertion.

    Science.gov (United States)

    Liao, Ping-Kuei; Liu, Kuan-Guan; Fang, Ching-Shiang; Liu, C W; Fackler, John P; Wu, Ying-Yann

    2011-09-01

    The hydrido copper(I) and silver(I) clusters incorporating 1,1-dicyanoethylene-2,2-dithiolate (i-MNT) ligands are presented in this paper. Reactions of M(I) (M = Cu, Ag) salts, [Bu(4)N](2)[S(2)CC(CN)(2)], with the anion sources ([Bu(4)N][BH(4)] for H(-), [Bu(4)N][BD(4)] for D(-)) in an 8:6:1 molar ratio in THF produce octanuclear penta-anionic Cu(I)/Ag(I) clusters, [Bu(4)N](5)[M(8)(X){S(2)CC(CN)(2)}(6)] (M = Cu, X = H, 1(H); X = D, 1(D); M = Ag, X = H, 2(H); X = D, 2(D)). They can also be produced from the stoichiometric reaction of M(8)(i-MNT)(6)(4-) with the ammonium borohydride. All four compounds have been fully characterized spectroscopically ((1)H and (13)C NMR, IR, UV-vis) and by elemental analyses. The deuteride-encapsulated Cu(8)/Ag(8) clusters of 1(D) and 2(D) are also characterized by (2)H NMR. X-ray crystal structures of 1(H) and 2(H) reveal a hydride-centered tetracapped tetrahedral Cu(8)/Ag(8) core, which is inscribed within an S(12) icosahedron formed by six i-MNT ligands, each in a tetrametallic-tetraconnective (μ(2), μ(2)) bonding mode. The encapsulated hydride in 2(H) is unequivocally characterized by both (1)H and (109)Ag NMR spectroscopies, and the results strongly suggest that the hydride is coupled to eight magnetically equivalent silver nuclei on the NMR time scale. Therefore, a fast interchange between the vertex and capping silver atoms in solution gives a plausible explanation for the perceived structural differences between the Ag(8) geometry deduced from the X-ray structure and the NMR spectra.

  13. Investigation of increased hydriding of guide tubes in Ringhals 2 during cycle startup

    International Nuclear Information System (INIS)

    There are two main sources for hydrogen uptake into Zr alloy components. Beside the uptake of hydrogen from the corrosion reaction, direct uptake of hydrogen from the PWR primary water is the second source and can occur under certain conditions. In Ringhals 2, two guide tubes broke during insertion of control rods in the pool during the outage in 1990 resulting from high hydrogen contents which were found in the Zry-4 guide tubes. The hydrogen content showed large variations between different guide tubes from the same assembly at the same axial elevation. In extreme cases, rims of massive hydrides were seen at the inner surface. In the most affected guide tubes, the oxide thickness at the ID was about 20 μm whereas normal oxide was only about 5 μm. Hot cell examination revealed that the hydrogen content was up to 3000 ppm (average in wall thickness) which means that the hydrogen pickup fraction was well above 100 %. This was a clear indication that a significant amount of hydrogen was stemming from a different source than corrosion. The inner surfaces of these particular guide tubes were grit-blasted with a stainless steel lance. The root-cause analysis revealed by SEM and GDOS that the grit-blasting with such a lance resulted in embedding small stainless steel particles at the guide tube inner surface which in-pile acted as 'hydrogen windows'. When Ni deposited on the surface during the start-up procedure, hydrogen was picked up catalytically after it was added to the coolant at about 150 deg. C. Autoclave tests simulating the start up of a PWR were used to demonstrate the increased hydrogen pickup. The tests showed that this type of accelerated hydriding can be reproduced in the laboratory with guide tube samples grit-blasted on the inside. A necessary condition was that Ni in the coolant was high during the start-up phase and hydrogen was added to the water before the formation of a protective oxide layer can prevent the hydrogen uptake. The tests revealed a

  14. Metal hydrides as electrode/catalyst materials for oxygen evolution/reduction in electrochemical devices

    Science.gov (United States)

    Bugga, Ratnakumar V. (Inventor); Halpert, Gerald (Inventor); Fultz, Brent (Inventor); Witham, Charles K. (Inventor); Bowman, Robert C. (Inventor); Hightower, Adrian (Inventor)

    1997-01-01

    An at least ternary metal alloy of the formula, AB.sub.(5-Y)X(.sub.y), is claimed. In this formula, A is selected from the rare earth elements, B is selected from the elements of groups 8, 9, and 10 of the periodic table of the elements, and X includes at least one of the following: antimony, arsenic, and bismuth. Ternary or higher-order substitutions, to the base AB.sub.5 alloys, that form strong kinetic interactions with the predominant metals in the base metal hydride are used to form metal alloys with high structural integrity after multiple cycles of hydrogen sorption.

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

    DEFF Research Database (Denmark)

    Poulsen, F.W.

    2001-01-01

    . H- is stable with respect to oxide and halide anions but, among cations only with respect to oxides and halides of strongly electropositive metals such as alkaline, alkaline-earth and main group III metals. H- is only stable in combination with transition metal ions of certain elements...... for this acceptor doped A(II)B(IV)O-3 model compound are solved without using the conventional Brouwer approximations, One case is presented where hydride formation is suppressed, and another case where it is promoted. Plots of concentration versus water and oxygen partial pressures show new interesting features...

  16. Pressure effects on the antiferromagnetic order of the hydride CeRuSiH

    Energy Technology Data Exchange (ETDEWEB)

    FernIndez, J Rodriguez; Rojas, D P; Sal, J C Gomez [DCITIMAC, Facultad de Ciencias, Universidad de Cantabria, 39005 Santander (Spain); Tence, S; Chevalier, B, E-mail: rodrigufj@unican.e [CNRS, Universite de Bordeaux, ICMCB, 87 Avenue Dr. A. Schweitzer, 33608 Pessac (France)

    2010-01-15

    The non-magnetic heavy fermion CeRuSi upon hydrogen absorption develops an antiferromagnetic behaviour, mainly due to the pronounced expansion of the unit cell. The effects of pressure on the {chi}(T) and M(H) curves of the hydride CeRuSiH up to 10.3 kbar are presented. Both, the Neel temperatures and the critical fields of the metamagnetic transitions, increase with pressure, whereas the net magnetization decreases. This evolution could be understood within the framework of the Doniach diagram.

  17. Heat capacity and magnetic phase diagram of the hydride CeRuSiH

    Energy Technology Data Exchange (ETDEWEB)

    Fernandez, J RodrIguez; Rojas, D P [CITIMAC, Facultad de Ciencias, Universidad de Cantabria, 39005 Santander (Spain); Gaudin, E; Chevalier, B, E-mail: rodrigufj@unican.es [CNRS, Universit de Bordeaux, ICMCB, 87 Avenue Dr. A. Schweitzer, 33608 Pessac (France)

    2011-01-01

    The hydride CeRuSiH exhibits antiferromagnetic order with two transitions at T{sub N1} = 7.5 and T{sub N2} = 3.1 K. Furthermore, magnetization measurements M (H) up to H = 45 kOe shows a metamagnetic double transition at low temperatures, suggesting a complex magnetic phase diagram. Here, we present magnetization measurements and heat capacity data up to 90 kOe, which allows as to complete the magnetic phase diagram. In addition, from the analysis of the heat capacity, we propose a model for the crystal field splitting.

  18. Electric Multipole Moments for Some First-Row Diatomic Hydride Molecules Metin Orbay and Telhat Ozdogan

    Institute of Scientific and Technical Information of China (English)

    Metin Orbay; Telhat Ozdogan

    2001-01-01

    As an example of the use of the analytical formulas derived for electric multipole moment integrals over STOs in our previous work (I.L Guseinov,et al.,J.Mol.Struct.(Theochem) 465 (1999) 5),the 2v-pole electric moments have been calculated for the ground electronic states of LiH,BH and FH of the first-row diatomic hydride molecules. Calculated electric multipole moment values are in agreement with literatures.By the use of these analytical formulas the 2v -pole moments for multiatomic molecules can be evaluated most efficiently and accurately by employing STOs as basis sets.

  19. K-shell Auger lifetime variation in doubly ionized Ne and first row hydrides.

    Science.gov (United States)

    Kolorenč, Přemysl; Averbukh, Vitali

    2011-10-01

    We consider 1s Auger decay in doubly (core-core and core-valence) ionized Ne and in the isoelectronic first row element hydrides. We show theoretically that the presence of the spectator inner valence vacancy leads to Auger lifetime variation of up to about a factor of 2, relative to the Auger lifetimes in the singly ionized species. The origin of this effect is traced to spin selection rules. Implications on the modelling of the radiation damage in strong x-ray fields are discussed.

  20. Dielectric barrier discharge plasma atomizer for hydride generation atomic absorption spectrometry-Performance evaluation for selenium

    Science.gov (United States)

    Duben, Ondřej; Boušek, Jaroslav; Dědina, Jiří; Kratzer, Jan

    2015-09-01

    Atomization of selenium hydride in a quartz dielectric barrier discharge (DBD) atomizer was optimized and its performance was compared to that of the externally heated quartz multiatomizer. Argon was found as the best DBD discharge gas employing a flow rate of 75 ml min- 1 Ar while the DBD power was optimized at 14 W. The detection limits reached 0.24 ng ml- 1 Se in the DBD and 0.15 ng ml- 1 Se in the multiatomizer. The tolerance of DBD to interferences is even better than with the multiatomizer.

  1. Study on the nature of interaction of furan with various hydrides.

    Science.gov (United States)

    Wu, Jun-Yong; Zhang, Jing-Chang; Wang, Zhao-Xu; Cao, Wei-Liang

    2007-11-01

    The nature of interactions of furan with various hydrides (Y) (Y=HF,HCl,H2O,H2S,NH3,PH3) is investigated using ab initio calculations. The contribution of attractive (electrostatic, inductive, and dispersive) and repulsive (exchange) components to the interactions energy is analyzed. HF, H2O, and NH3 favor sigma o-type H bonding, while HCl, H2S, and PH3 favor pi-type H bonding. Interaction energy decomposition reveals that sigma o-type complexes interactions are predominantly electrostatic in nature, while the dispersion and electrostatic interactions dominate the pi-type complexes.

  2. Kinetic equation for the reaction of titanium tetrachloride with hydride functional groups of diamond

    Energy Technology Data Exchange (ETDEWEB)

    Zhidkov, A.B.; Smirnov, E.P.

    1989-02-01

    This work is devoted to the study of the kinetics of the reaction of titanium tetrachloride with the hydride functional groups of diamond. The research was performed on submicron powders of ASM 0.7/0.3 grade synthetic diamond with a specific surface area of 8.0 m/sup 2//g as measured from the adsorption of nitrogen. The reaction was carried out in a flow-through quartz reactor in a flow of dry He. The content of the titanium in the samples was determined by a photocolorimetric method. A kinetic equation for the reaction of diamond with titanium tetrachloride was found on the basis of a statistical approach.

  3. Ab initio analysis of magnetovolume versus chemical effects in CeRuSi and its hydride

    Science.gov (United States)

    Matar, Samir F.

    2007-03-01

    The change from heavy fermion to antiferromagnetic behavior of intermetallic system CeRuSi upon hydrogenation is addressed on bases of lattice expansion and chemical bonding effects within the density-functional theoretical framework using all electron scalar-relativistic augmented spherical wave method. While no magnetic moment develops in the 111 system, from total-energy differences, the hydride is found to be stable as an antiferromagnet in the ground state, in agreement with experiment. The role of anisotropic lattice expansion induced by hydrogen insertion is shown to be prevailing over the chemical bonding between hydrogen and the metallic species especially cerium.

  4. Nitrogen hydrides in the cold envelope of IRAS16293-2422

    OpenAIRE

    Hily-Blant, Pierre; Maret, Sébastien; Bacmann, A.; Bottinelli, Sandrine; Parise, Bérengère; Caux, Emmanuel; Faure, Alexandre

    2010-01-01

    Nitrogen is the fifth most abundant element in the Universe, yet the gas-phase chemistry of N-bearing species remains poorly understood. Nitrogen hydrides are key molecules of nitrogen chemistry. Their abundance ratios place strong constraints on the production pathways and reaction rates of nitrogen-bearing molecules. We observed the class 0 protostar IRAS16293-2422 with the heterodyne instrument HIFI, covering most of the frequency range from 0.48 to 1.78~THz at high spectral resolution. Th...

  5. A low cost igniter utilizing an SCB and titanium sub-hydride potassium perchlorate pyrotechnic

    Science.gov (United States)

    Bickes, R. W., Jr.; Grubelich, M. C.; Hartman, J. K.; McCampbell, C. B.; Churchill, J. K.

    1994-01-01

    A conventional NSI (NASA Standard Initiator) normally employs a hot-wire ignition element to ignite ZPP (zirconium potassium perchlorate). With minor modifications to the interior of a header similar to an NSI device to accommodate an SCB (semiconductor bridge), a low cost initiator was obtained. In addition, the ZPP was replaced with THKP (titanium sub-hydride potassium perchlorate) to obtain increased overall gas production and reduced static-charge sensitivity. This paper reports on the all-fire and no-fire levels obtained and on a dual mix device that uses THKP as the igniter mix and a thermite as the output mix.

  6. Reversible hydrogen storage properties of Ti-doped lithium aluminium hydride

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    In this paper our work on lithium aluminium hydride doping with Ti(OBu)4by mechanical milling was showed. Its thermodynamic and kinetics were enhanced greatly and its reversible hydrogen storage capacity could reach 3. 0% (mass fraction). From the X-ray diffraction (XRD) patterns, we found that a lot of LiAlH4 had been decomposed to Li3AlH6 and Al. The catalyst Ti (OBu)4 couldn't be found after ball-milling, instead TiAl3 appeared. But the locations of Ti atoms are still not determined.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1994-01-01

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

  8. Experimental design and simulation of a metal hydride hydrogen storage system

    Science.gov (United States)

    Gadre, Sarang Ajit

    Metal hydrides, as a hydrogen storage medium, have been under consideration for many years because they have the ability to store hydrogen reversibly in the solid state at relatively low pressures and ambient temperatures. The utility of metal hydrides as a hydrogen storage medium was demonstrated recently by the Savannah River Technology Center (SRTC) in an on-board hydrogen storage system for a hybrid electric bus project. The complex geometry and the intricate design of the SRTC bed presents quite a challenge to the development of a mathematical model that can be used for design and optimization. In a new approach introduced here, the reversible reaction kinetics and the empirical Van't Hoff relationship used in a typical reactor model are replaced by a solid phase diffusion equation and one of the two semi-empirical equilibrium P-C-T relationships based on modified virial and composite Langmuir isotherm expressions. Starting with the simplest mathematical formulation, which resulted in an analytical expression, various models were developed and successively improved by relaxing certain assumptions, eventually resulting in the most rigorous model yet developed for this system. All of these models were calibrated using experimental pressure and temperature histories obtained from a bench scale hydrogen storage test facility. The heat and mass transfer coefficients or the thermal conductivity were the only adjustable parameters in these models. A design of experiments approach was also used for studying the effect of various factors on the performance of this bench scale hydrogen storage unit. Overall, the results of this study demonstrated that even a fairly simple numerical model could do a reasonable job in predicting the discharge behavior of a fairly complicated, metal hydride hydrogen storage bed over a wide range of operating conditions. The more rigorous 2-D model gave considerable insight into the dynamics of the hydrogen discharge process from an

  9. Solid-state structures and properties of scandium hydride; hydrogen storage and switchable mirrors application

    Science.gov (United States)

    Khodja, Khadidja; Bouhadda, Youcef; Seddik, Larbi; Benyelloul, Kamel

    2016-05-01

    First-principles calculation has been performed on the rare earth hydride ScH2 for hydrogen storage and switchable mirror applications, using the pseudo-potentials and plane waves based on the density-functional theory (DFT). The electronic and structural properties are studied within both local-density and generalized gradient approximations for exchange energy. The formation energy and the optical properties have been investigated and discussed. Our calculated results are generally in good agreement with theoretical and experimental data. Contribution to the topical issue "Materials for Energy Harvesting, Conversion and Storage (ICOME 2015) - Elected submissions", edited by Jean-Michel Nunzi, Rachid Bennacer and Mohammed El Ganaoui

  10. Analysis of Mercury-Rich plants and mine tailings using the Hydride-Generation AAS method

    OpenAIRE

    Fábio Netto Moreno; Christopher Anderson; Robert Stewart; Brett Robinson

    2009-01-01

    A hydride-generation atomic absorption spectroscopy (AAS) method was developed for the analysis of total Hg in liquid matrices of mercury-rich plants and mine tailings samples. The detection limit for this method was as low as 11.4 ng/mL. The reproducibility of the mercury signals (in terms of relative standard deviation) was 4.6%. Accuracy of the method was verified by analyses of deionised water samples spiked with HgCl2 and HgNO3. Recovery values for total mercury ranged from 88.5 to 94.3%...

  11. Hydride bridge in [NiFe]-hydrogenase observed by nuclear resonance vibrational spectroscopy

    OpenAIRE

    Ogata, Hideaki; Krämer, Tobias; Wang, Hongxin; Schilter, David; Pelmenschikov, Vladimir; van Gastel, Maurice; Neese, Frank; Rauchfuss, Thomas B.; Gee, Leland B.; Scott, Aubrey D.; Yoda, Yoshitaka; Tanaka, Yoshihito; Lubitz, Wolfgang; Cramer, Stephen P.

    2015-01-01

    The metabolism of many anaerobes relies on [NiFe]-hydrogenases, whose characterization when bound to substrates has proven non-trivial. Presented here is direct evidence for a hydride bridge in the active site of the 57Fe-labeled fully reduced Ni-R form of Desulfovibrio vulgaris Miyazaki F (DvMF) [NiFe]-hydrogenase. A unique ‘wagging’ mode involving H− motion perpendicular to the Ni(μ-H)57Fe plane was studied using 57Fe-specific nuclear resonance vibrational spectroscopy (NRVS) and density fu...

  12. Modeling and Simulation of Used Nuclear Fuel During Transportation with Consideration of Hydride Effects and Cyclic Fatigue

    Energy Technology Data Exchange (ETDEWEB)

    Chakraborty, Pritam [Idaho National Lab. (INL), Idaho Falls, ID (United States); Sabharwall, Piyush [Idaho National Lab. (INL), Idaho Falls, ID (United States); Spears, Robert Edward [Idaho National Lab. (INL), Idaho Falls, ID (United States); Coleman, Justin Leigh [Idaho National Lab. (INL), Idaho Falls, ID (United States); Sener, Kadir [STANEX (United States); Varma, Amit H. [STANEX (United States)

    2015-09-30

    The objective of this work is to understand the integrity of Used Nuclear Fuel (UNF) during transportation. Previous analysis work has been performed to look at the integrity of UNF during transportation but these analyses have neglected to analyze the effect of hydrides and flaws (fracture mechanics models to capture radial cracking in the cladding). In this study, the clad regions of interest are near the pellet-pellet interfaces. These regions can experience more complex stress-states than the rest of the clad during cooling and have a greater possibility to develop radially reoriented hydrides during vacuum drying.

  13. Study of δ-hydrides in Ti-2Al-2.5Zr and Ti-4Al-2V alloys

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The α alloy Ti-2Al-2.5Zr and near α alloy Ti-4Al-2V were hydrogenated to various levels. The morphology,orientation relation (OR), and habit plane of the hydrides were studied by means of transmission electron microscopy (TEM). It was found that in the two alloys most of the precipitates are δ-hydrides which have fcc structure with the lattice parameter a = 0.44 nm. Two basic orientation relationships and habit planes of the precipitates are determined. Twin structure was observed in both alloys.

  14. Nickel/metal hydride technology for consumer and electric vehicle batteries—a review and up-date

    Science.gov (United States)

    Dhar, S. K.; Ovshínsky, S. R.; Gifford, P. R.; Corrigan, D. A.; Fetcenko, M. A.; Venkatesan, S.

    Nickel/metal hydride batteries today represent the fastest growing market segment for rechargeable batteries due to the high energy density and more environmentally acceptable chemistry offered by this technology. The high energy density of nickel/metal hydride batteries coupled with high power density and long cycle life make this battery chemistry a key enabling technology for practical electric vehicles, including cars, vans, trucks, and other forms of transportation such as scooters, bicycles, and three-wheelers. This paper provides a review of Ovonic technology and up-dates recent developments in materials and cell development for both consumer electronic and EV applications, and highlights areas for future development.

  15. Heterogeneous reduction of carbon dioxide by hydride-terminated silicon nanocrystals

    Science.gov (United States)

    Sun, Wei; Qian, Chenxi; He, Le; Ghuman, Kulbir Kaur; Wong, Annabelle P. Y.; Jia, Jia; Jelle, Abdinoor A.; O'Brien, Paul G.; Reyes, Laura M.; Wood, Thomas E.; Helmy, Amr S.; Mims, Charles A.; Singh, Chandra Veer; Ozin, Geoffrey A.

    2016-08-01

    Silicon constitutes 28% of the earth's mass. Its high abundance, lack of toxicity and low cost coupled with its electrical and optical properties, make silicon unique among the semiconductors for converting sunlight into electricity. In the quest for semiconductors that can make chemicals and fuels from sunlight and carbon dioxide, unfortunately the best performers are invariably made from rare and expensive elements. Here we report the observation that hydride-terminated silicon nanocrystals with average diameter 3.5 nm, denoted ncSi:H, can function as a single component heterogeneous reducing agent for converting gaseous carbon dioxide selectively to carbon monoxide, at a rate of hundreds of μmol h-1 g-1. The large surface area, broadband visible to near infrared light harvesting and reducing power of SiH surface sites of ncSi:H, together play key roles in this conversion. Making use of the reducing power of nanostructured hydrides towards gaseous carbon dioxide is a conceptually distinct and commercially interesting strategy for making fuels directly from sunlight.

  16. DFT modeling of the electronic and magnetic structures and chemical bonding properties of intermetallic hydrides

    International Nuclear Information System (INIS)

    This thesis presents an ab initio study of several classes of intermetallics and their hydrides. These compounds are interesting from both a fundamental and an applied points of view. To achieve this aim two complementary methods, constructed within the DFT, were chosen: (i) pseudo potential based VASP for geometry optimization, structural investigations and electron localization mapping (ELF), and (ii) all-electrons ASW method for a detailed description of the electronic structure, chemical bonding properties following different schemes as well as quantities depending on core electrons such as the hyperfine field. A special interest is given with respect to the interplay between magneto-volume and chemical interactions (metal-H) effects within the following hydrided systems: binary Laves (e.g. ScFe2) and Haucke (e.g. LaNi5) phases on one hand, and ternary cerium based (e.g. CeRhSn) and uranium based (e.g. U2Ni2Sn) alloys on the other hand. (author)

  17. A Novel Zr-1Nb Alloy and a New Look at Hydriding

    Energy Technology Data Exchange (ETDEWEB)

    Robert D. Mariani; James I. Cole; Assel Aitkaliyeva

    2013-09-01

    A novel Zr-1Nb has begun development based on a working model that takes into account the hydrogen permeabilities for zirconium and niobium metals. The beta-Nb secondary phase particles (SPPs) in Zr-1Nb are believed to promote more rapid hydrogen dynamics in the alloy in comparison to other zirconium alloys. Furthermore, some hydrogen release is expected at the lower temperatures corresponding to outages when the partial pressure of H2 in the coolant is less. These characteristics lessen the negative synergism between corrosion and hydriding that is otherwise observed in cladding alloys without niobium. In accord with the working model, development of nanoscale precursors was initiated to enhance the performance of existing Zr-1Nb alloys. Their characteristics and properties can be compared to oxide-dispersion strengthened alloys, and material additions have been proposed to zirconium-based LWR cladding to guard further against hydriding and to fix the size of the SPPs for microstructure stability enhancements. A preparative route is being investigated that does not require mechanical alloying, and 10 nanometer molybdenum particles have been prepared which are part of the nanoscale precursors. If successful, the approach has implications for long term dry storage of used fuel and for new routes to nanoferritic and ODS alloys.

  18. Metal hydride hydrogen and heat storage systems as enabling technology for spacecraft applications

    Energy Technology Data Exchange (ETDEWEB)

    Reissner, Alexander, E-mail: reissner@fotec.at [FOTEC Forschungs- und Technologietransfer GmbH, Viktor Kaplan Straße 2, 2700 Wiener Neustadt (Austria); University of Applied Sciences Wiener Neustadt, Johannes Gutenberg-Straße 3, 2700 Wiener Neustadt (Austria); Pawelke, Roland H.; Hummel, Stefan; Cabelka, Dusan [FOTEC Forschungs- und Technologietransfer GmbH, Viktor Kaplan Straße 2, 2700 Wiener Neustadt (Austria); Gerger, Joachim [University of Applied Sciences Wiener Neustadt, Johannes Gutenberg-Straße 3, 2700 Wiener Neustadt (Austria); Farnes, Jarle, E-mail: Jarle.farnes@prototech.no [CMR Prototech AS, Fantoftvegen 38, PO Box 6034, 5892 Bergen (Norway); Vik, Arild; Wernhus, Ivar; Svendsen, Tjalve [CMR Prototech AS, Fantoftvegen 38, PO Box 6034, 5892 Bergen (Norway); Schautz, Max, E-mail: max.schautz@esa.int [European Space Agency, ESTEC – Keplerlaan 1, 2201 AZ Noordwijk Zh (Netherlands); Geneste, Xavier, E-mail: xavier.geneste@esa.int [European Space Agency, ESTEC – Keplerlaan 1, 2201 AZ Noordwijk Zh (Netherlands)

    2015-10-05

    Highlights: • A metal hydride tank concept for heat and hydrogen storage is presented. • The tank is part of a closed-loop reversible fuel cell system for space application. • For several engineering issues specific to the spacecraft application, solutions have been developed. • The effect of water contamination has been approximated for Ti-doped NaAlH{sub 4}. • A novel heat exchanger design has been realized by Selective Laser Melting. - Abstract: The next generation of telecommunication satellites will demand a platform payload performance in the range of 30+ kW within the next 10 years. At this high power output, a Regenerative Fuel Cell Systems (RFCS) offers an efficiency advantage in specific energy density over lithium ion batteries. However, a RFCS creates a substantial amount of heat (60–70 kJ per mol H{sub 2}) during fuel cell operation. This requires a thermal hardware that accounts for up to 50% of RFCS mass budget. Thus the initial advantage in specific energy density is reduced. A metal hydride tank for combined storage of heat and hydrogen in a RFCS may overcome this constraint. Being part of a consortium in an ongoing European Space Agency project, FOTEC is building a technology demonstrator for such a combined hydrogen and heat storage system.

  19. 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.

  20. Separation of trace antimony and arsenic prior to hydride generation atomic absorption spectrometric determination

    International Nuclear Information System (INIS)

    A separation method utilizing a synthetic zeolite (mordenite) was developed in order to eliminate the gas phase interference of Sb(III) on As(III) during quartz furnace hydride generation atomic absorption spectrometric (HGAAS) determination. The efficiency of the proposed separation method in the reduction of suppression effects of transition metal ions on As(III) signal was also investigated. Among the volatile hydride-forming elements and their different oxidation states tested (Sb(III), Sb(V), Se(IV), Se(VI), Te(IV), and Te(VI)), only Sb(III) was found to have a signal depression effect even at low (μg l-1) concentrations under the experimental conditions employed. It has been shown that mordenite adsorbs Sb(III) quantitatively, even at a concentration of 1000 μg l-1, at pHs greater than two, and also, it reduces the initial concentrations of the transition metal ions to lower levels which can be tolerated in many studies. The adsorption of Sb(III) on mordenite follows the Freundlich isotherm and is endothermic in nature

  1. Organic solvents as interferents in arsenic determination by hydride generation atomic absorption spectrometry with flame atomization

    Science.gov (United States)

    Karadjova, Irina B.; Lampugnani, Leonardo; Dědina, Jiri; D'Ulivo, Alessandro; Onor, Massimo; Tsalev, Dimiter L.

    2006-05-01

    Interference effects of various organic solvents miscible with water on arsenic determination by hydride generation atomic absorption spectrometry have been studied. Arsine was chemically generated in continuous flow hydride generation system and atomized by using a flame atomizer able to operate in two modes: miniature diffusion flame and flame-in-flame. The effects of experimental variables and atomization mode were investigated: tetrahydroborate and hydrochloric acid concentrations, argon, hydrogen and oxygen supply rates for the microflame, and the distance from the atomization region to the observation zone. The nature of the species formed in the flame due to the pyrolysis of organic solvent vapors entering the flame volume together with arsine is discussed. The observed signal depression in the presence of organic solvents has been mainly attributed to the atomization interference due to heterogeneous gas-solid reaction between the free arsenic atoms and finely dispersed carbon particles formed by carbon radicals recombination. The best tolerance to interferences was obtained by using flame-in-flame atomization (5-10 ml min - 1 of oxygen flow rate), together with higher argon and hydrogen supply rates and elevated observation heights.

  2. A method for determining total oxygen in lithium hydride (deuteride) by pulse melt-gas chromatography

    International Nuclear Information System (INIS)

    A method for determining total oxygen in the lithium hydride (deuteride) by pulse melt helium atmosphere carryover and GC thermal conductivity are described. The sample in tin leaf clad is put into a graphite crucible with a cap. Firstly, the sample is decomposed by heat at about 660 degree C, and the multiform oxygen in the sample is reserved in tin-lithium alloy by the Li2O form. Then, the alloy pass through reduction with carbon at about 2200 degree C high temperature pulse, and the oxygen in the alloy is released in carbon monoxide form. It is carried into chromatographic column of active carbon by the helium atmosphere, and determined by the thermal conductivity sequentially. The sample size of the method is 5-15 mg. The detection range is 0.30% - 5.00%, and the relative standard deviation is between 15% - 3.6%, correspondingly. The recovery rate of the oxygen that is determined by lithium carbonate adding to lithium hydride (deuteride) is 86% - 116%

  3. Enhancement in dehydriding performance of magnesium hydride by iron incorporation: A combined experimental and theoretical investigation

    Science.gov (United States)

    Chen, Haipeng; Yu, Hao; Zhang, Qianqian; Liu, Bogu; Liu, Pei; Zhou, Xinpei; Han, Zongying; Zhou, Shixue

    2016-08-01

    Structural change and dehydriding mechanism of MgH2 with atomic Fe incorporation from reactive ball milling are characterized and simulated by first-principles calculation. Two kinds of hydrides β- and γ-MgH2 are formed from Mg powders under hydrogen atmosphere by 3.0 h of milling with pretreated anthracite as milling aid. Experimental studies suggest that the atomic Fe can be incorporated onto MgH2 surface by the shearing effect of Fe-based milling balls on Mg/MgH2 particles. The incorporated Fe has a high dispersity on MgH2 surface and can form atomic clusters FeH4/FeH2 by combining with H anions. The dehydriding reaction of the Fe-incorporated MgH2 begins at hydride surface and shows an enhanced performance with apparent activation energy of 110.3 kJ mol-1. Theoretical studies suggest that the incorporated Fe can act as a bridge that contributes to electron transfer from H anion to Mg cation before H2 molecule formation. The intrinsic reason of atomic Fe in catalyzing dehydriding reaction of MgH2 lies in its moderate strength of electron attraction.

  4. Effects of the Electronic Doping In the Stability of the Metal Hydride NaH

    Science.gov (United States)

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

    2015-03-01

    Despite metal hydrides light weight and high hydrogen volumetric densities, the Hydrogen desorption process requires excessively high temperatures due to their high stability. Attempts for improvement the hydrogenation properties have been focus on the introduction of defects, impurities and doping on the metal hydride. We present a systematic study of the electronic doping effects on the stability of a model system, NaH doped with magnesium, forming the alloying system Na1-xMgxH. We use the density functional theory (DFT) and the self-consistent version of the virtual crystal approximation (VCA) to model the doping of NaH with Mg. The evolution of the ground state structural and electronic properties is analyzed as a function of Mg-content. The full-phonon dispersion, calculated by the linear response theory (LRT) and density functional perturbation theory (DFPT), is analyzed for several Mg-concentrations, paying special attention to the crystal stability and the correlations with the electronic structure. Applying the quasiharmonic approximation (QHA), the free energy from zero-point motion is obtained, and its influence on the properties under study is analyzed. This work is partially supported by the VIEP-BUAP (OMPS-EXC14-I) and CONACYT-Mexico (No. 221807) projects.

  5. Metal hydride/chemical heat-pump development project, phase 1

    Science.gov (United States)

    Argabright, T. A.

    1982-02-01

    The metal hydride/chemical heat pump (MHHP) is a chemical heat pump containing two hydrides for the storage and/or recovery of thermal energy. It utilizes the heat of reaction of hydrogen with specific metal alloys. The MHHP design can be tailored to provide heating and/or cooling or temperature upgrading over a wide range of input and ambient temperatures. The system can thus be used with a variety of heat sources including waste heat, solar energy or a fossil fuel. The conceptual design of the MHHP was developed. A national market survey including a study of applications and market sectors was conducted. The technical tasks including conceptual development, thermal and mechanical design, laboratory verification of design and material performance, cost analysis and the detailed design of the Engineering Development Test Unit (EDTU) were performed. As a result of the market study, the temperature upgrade cycle of the MHHP was chosen for development. Operating temperature ranges for the upgrader were selected to be from 70 to 1100 C (160 to 2300 F) for the source heat and 140 to 1900 C (280 to 3750 F) for the product heat.

  6. First-Principles Modeling of Hydrogen Storage in Metal Hydride Systems

    Energy Technology Data Exchange (ETDEWEB)

    J. Karl Johnson

    2011-05-20

    The objective of this project is to complement experimental efforts of MHoCE partners by using state-of-the-art theory and modeling to study the structure, thermodynamics, and kinetics of hydrogen storage materials. Specific goals include prediction of the heats of formation and other thermodynamic properties of alloys from first principles methods, identification of new alloys that can be tested experimentally, calculation of surface and energetic properties of nanoparticles, and calculation of kinetics involved with hydrogenation and dehydrogenation processes. Discovery of new metal hydrides with enhanced properties compared with existing materials is a critical need for the Metal Hydride Center of Excellence. New materials discovery can be aided by the use of first principles (ab initio) computational modeling in two ways: (1) The properties, including mechanisms, of existing materials can be better elucidated through a combined modeling/experimental approach. (2) The thermodynamic properties of novel materials that have not been made can, in many cases, be quickly screened with ab initio methods. We have used state-of-the-art computational techniques to explore millions of possible reaction conditions consisting of different element spaces, compositions, and temperatures. We have identified potentially promising single- and multi-step reactions that can be explored experimentally.

  7. Superconductivity and the structural phase transitions in palladium hydride and palladium deuteride

    International Nuclear Information System (INIS)

    The results of two experimental studies of the superconducting transition temperature, T/sub c/, of palladium hydride, PdH/sub x/, and palladium deuteride, PdD/sub x/, are presented. In the first study, the superconducting transition temperature of PdH/sub x/(D/sub x/) is studied as a function of H(D) concentration, x, in the temperature range from 0.2 K to 4K. The data join smoothly with those reported previously by Miller and Satterthwaite at higher temperatures, and the composite data are described by the empirical relation T/sub c/ = 150.8 (x-x/sub o/)2244, where x/sub o/ = 0.715 for hydride samples and 0.668 for deuteride samples. The results, when compared with the theoretical predictions of Klein and Papaconstantopoulos, et al., raise questions about the validity of their explanation of the reverse isotope effect, which is based solely on a difference in force constants. In the second study, the effect of the order-disorder structural transition associated with the 50 K anomaly on the superconductivity of PdH/sub x/(D/sub x/) is investigated. Samples were quenched to low temperatures in the disordered state, and their transition temperatures measured. The samples were then annealed just below the anomaly temperature, and the ordering process followed by monitoring the change in sample resistance. The transition temperatures in the ordered state were then measured

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

    CERN Document Server

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

    2013-01-01

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

  9. Determination of tellurium by hydride generation with in situ trapping flame atomic absorption spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Matusiewicz, H.; Krawczyk, M. [Politechn Poznanska, Poznan (Poland)

    2007-03-15

    The analytical performance of coupled hydride generation - integrated atom trap (HG-IAT) atomizer flame atomic absorption spectrometry (FAAS) system was evaluated for determination of Te in reference material (GBW 07302 Stream Sediment), coal fly ash and garlic. Tellurium, using formation of H{sub 2}Te vapors, is atomized in air-acetylene flame-heated IAT. A new design HG-IAT-FAAS hyphenated technique that would exceed the operational capabilities of existing arrangernents (a water-cooled single silica tube, double-slotted quartz tube or an 'integrated trap') was investigated. An improvement in detection limit was achieved compared with using either of the above atom trapping techniques separately. The concentration detection limit, defined as 3 times the blank standard deviation (3{sigma}), was 0.9 ng mL{sup -1} for Te. For a 2 min in situ preconcentration time (sample volume of 2 mL), sensitivity enhancement compared to flame AAS, was 222 fold, using the hydride generation atom trapping technique. The sensitivity can be further improved by increasing the collection time. The precision, expressed as RSD, was 7.0% (n = 6) for Te. The accuracy of the method was verified using a certified reference material (GBW 07302 Stream Sediment) by aqueous standard calibration curves. The measured Te contents of the reference material was in agreement with the information value. The method was successfully applied to the determination of tellurium in coal fly ash and garlic.

  10. Numerical investigation of coupled heat and mass transfer during desorption of hydrogen in metal hydride beds

    Energy Technology Data Exchange (ETDEWEB)

    Muthukumar, P.; Satheesh, A.; Madhavakrishna, U.; Dewan, Anupam [Department of Mechanical Engineering, Indian Institute of Technology Guwahati, Guwahati 781039, Assam (India)

    2009-01-15

    This paper presents a numerical investigation of two-dimensional coupled heat and mass transfer processes in MmNi{sub 4.6}Fe{sub 0.4} and MmNi{sub 4.6}Al{sub 0.4} based metal hydride beds of cylindrical configuration during desorption of hydrogen using a commercial software FLUENT 6.1.22. Temperature and concentration profiles at different radial locations, variation of average bed temperature and amount of hydrogen desorbed are presented at different hot fluid temperatures and bed thicknesses ranging from 30 to 50 C and 5 to 15 mm, respectively. The numerical results show that the dehydriding process for both the alloys depends on the temperature distribution in the metal hydride bed. At a given hot fluid temperature of 50 C, MmNi{sub 4.6}Fe{sub 0.4} and MmNi{sub 4.6}Al{sub 0.4} desorb the maximum hydrogen of about 1.11 and 1.28 wt%, respectively at the supply conditions of 30 bar and 25 C. The present computational results are also compared with the experimental data reported in the literature and a good agreement was found between the two. (author)

  11. Two-Dimensional Boron Hydride Sheets: High Stability, Massless Dirac Fermions, and Excellent Mechanical Properties.

    Science.gov (United States)

    Jiao, Yalong; Ma, Fengxian; Bell, John; Bilic, Ante; Du, Aijun

    2016-08-22

    Two-dimensional (2D) boron sheets have been successfully synthesized in recent experiments, however, some important issues remain, including the dynamical instability, high energy, and the active surface of the sheets. In an attempt to stabilize 2D boron layers, we have used density functional theory and global minimum search with the particle-swarm optimization method to predict four stable 2D boron hydride layers, namely the C2/m, Pbcm, Cmmm, and Pmmn sheets. The vibrational normal mode calculations reveal all these structures are dynamically stable, indicating potential for successful experimental synthesis. The calculated Young's modulus indicates a high mechanical strength for the C2/m and Pbcm phases. Most importantly, the C2/m, Pbcm, and Pmmn structures exhibit Dirac cones with massless Dirac fermions and the Fermi velocities for the Pbcm and Cmmm structures are even higher than that of graphene. The Cmmm phase is reported as the first discovery of Dirac ring material among boron-based 2D structures. The unique electronic structure of the 2D boron hydride sheets makes them ideal for nanoelectronics applications. PMID:27460282

  12. Heterogeneous reduction of carbon dioxide by hydride-terminated silicon nanocrystals

    Science.gov (United States)

    Sun, Wei; Qian, Chenxi; He, Le; Ghuman, Kulbir Kaur; Wong, Annabelle P. Y.; Jia, Jia; Jelle, Abdinoor A.; O'Brien, Paul G.; Reyes, Laura M.; Wood, Thomas E.; Helmy, Amr S.; Mims, Charles A.; Singh, Chandra Veer; Ozin, Geoffrey A.

    2016-01-01

    Silicon constitutes 28% of the earth's mass. Its high abundance, lack of toxicity and low cost coupled with its electrical and optical properties, make silicon unique among the semiconductors for converting sunlight into electricity. In the quest for semiconductors that can make chemicals and fuels from sunlight and carbon dioxide, unfortunately the best performers are invariably made from rare and expensive elements. Here we report the observation that hydride-terminated silicon nanocrystals with average diameter 3.5 nm, denoted ncSi:H, can function as a single component heterogeneous reducing agent for converting gaseous carbon dioxide selectively to carbon monoxide, at a rate of hundreds of μmol h−1 g−1. The large surface area, broadband visible to near infrared light harvesting and reducing power of SiH surface sites of ncSi:H, together play key roles in this conversion. Making use of the reducing power of nanostructured hydrides towards gaseous carbon dioxide is a conceptually distinct and commercially interesting strategy for making fuels directly from sunlight. PMID:27550234

  13. Atomic absorption determination, in metal sulphide concentrates, of the elements that form gaseous hydrides

    International Nuclear Information System (INIS)

    An account is given of the investigational work on the determination of trace amounts of arsenic, antimony, bismuth, germanium, selenium, and tellurium by the technique using hydride generation and atomic-absorption spectrophotometry. The gaseous hydride is generated by reduction with sodium borohydride, and is subsequently swept by a flow of nitrogen into an air-entrained hydrogen-nitrogen flame. The generation equipment used is simple and inexpensive, and can be readily assembled in most laboratories. The optimum parameters were determined for each element. The effects of 31 probable interfering elements were investigated, and it was found that, although the majority did not interfere, severe interference was encountered when copper, nickel, and the noble metals were present. Methods for the elimination of copper and nickel were developed to allow the determination of arsenic, antimony, bismuth, selenium, and tellurium at the lower parts-per-million level in metal sulphide concentrates with an acceptable accuracy and precision. The determination of microgram amounts of germanium was found to be unsatisfactory

  14. Complex hydrides as room-temperature solid electrolytes for rechargeable batteries

    Science.gov (United States)

    de Jongh, P. E.; Blanchard, D.; Matsuo, M.; Udovic, T. J.; Orimo, S.

    2016-03-01

    A central goal in current battery research is to increase the safety and energy density of Li-ion batteries. Electrolytes nowadays typically consist of lithium salts dissolved in organic solvents. Solid electrolytes could facilitate safer batteries with higher capacities, as they are compatible with Li-metal anodes, prevent Li dendrite formation, and eliminate risks associated with flammable organic solvents. Less than 10 years ago, LiBH4 was proposed as a solid-state electrolyte. It showed a high ionic conductivity, but only at elevated temperatures. Since then a range of other complex metal hydrides has been reported to show similar characteristics. Strategies have been developed to extend the high ionic conductivity of LiBH4 down to room temperature by partial anion substitution or nanoconfinement. The present paper reviews the recent developments in complex metal hydrides as solid electrolytes, discussing in detail LiBH4, strategies towards for fast room-temperature ionic conductors, alternative compounds, and first explorations of implementation of these electrolytes in all-solid-state batteries.

  15. High Performance Operation Control for Heat Driven Heat Pump System using Metal Hydride

    Science.gov (United States)

    Okamoto, Hideyuki; Masuda, Masao; Kozawa, Yoshiyuki

    lt is recognized that COP of heat driven heat pump system using metal hydride is 0.3-0.4 in general. In order to rise COP, we have proposed two kinds of specific operation control; the control of cycle change time according to cold heat load and the control of cooling water temperature according to outside air wet-bulb temperature. The characteristics of the heat pump system using metal hydride have grasped by various experiments and simulations. The validity of the simulation model has been confirmed by comparing with experimental results. As results of the simulations programmed for the actual operation control month by month, yearly COP has risen till 0.5-0.6 for practical scale air-conditioning system without regard for the building use. By the operation control hour by hour, yearly COP has risen till 0.6-0.65. Moreover, in the office building case added 40% sensible heat recovery, yearly COP has risen more than 0.8.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-09-01

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

  17. Ultratrace determination of tin by hydride generation in-atomizer trapping atomic absorption spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Průša, Libor [Institute of Analytical Chemistry of the ASCR, v. v. i., Veveří 97, 602 00 Brno (Czech Republic); Charles University in Prague, Faculty of Science, Department of Analytical Chemistry, Hlavova 8, Prague 2, CZ 128 43 Czech Republic (Czech Republic); Dědina, Jiří [Institute of Analytical Chemistry of the ASCR, v. v. i., Veveří 97, 602 00 Brno (Czech Republic); Kratzer, Jan, E-mail: jkratzer@biomed.cas.cz [Institute of Analytical Chemistry of the ASCR, v. v. i., Veveří 97, 602 00 Brno (Czech Republic)

    2013-12-04

    Graphical abstract: -- Highlights: •In-atomizer trapping HG-AAS was optimized for Sn. •A compact quartz trap-and-atomizer device was employed. •Generation, preconcentration and atomization steps were investigated in detail. •Hundred percent preconcentration efficiency for tin was reached. •Routine analytical method was developed for Sn determination (LOD of 0.03 ng mL{sup −1} Sn). -- Abstract: A quartz multiatomizer with its inlet arm modified to serve as a trap (trap-and-atomizer device) was employed to trap tin hydride and subsequently to volatilize collected analyte species with atomic absorption spectrometric detection. Generation, atomization and preconcentration conditions were optimized and analytical figures of merit of both on-line atomization as well as preconcentration modes were quantified. Preconcentration efficiency of 95 ± 5% was found. The detection limits reached were 0.029 and 0.14 ng mL{sup −1} Sn, respectively, for 120 s preconcentration period and on-line atomization mode without any preconcentration. The interference extent of other hydride forming elements (As, Se, Sb and Bi) on tin determination was found negligible in both modes of operation. The applicability of the developed preconcentration method was verified by Sn determination in a certified reference material as well as by analysis of real samples.

  18. Characteristics of Hydrogen Storage Alloy Mg2Ni Produced by Hydriding Combustion Synthesis

    Institute of Scientific and Technical Information of China (English)

    Qian LI; Qin LIN; Lijun JIANG; Kou-chih CHOU; Feng ZHAN; Qiang ZHENG

    2004-01-01

    A high activity and large capacity of hydrogen storage alloy Mg2Ni by hydriding combustion synthesis was investigatedby means of pressure composition isotherms, X-ray diffraction and scanning electron microscopy. The results showedthat the maximum hydrogen absorption capacity of Mg2Ni is 3.25 mass fraction at 523 K, just after synthesis withoutany activation. The relationships between the equilibrium plateau pressure and the temperature for Mg2Ni were lgp(0.1 Mpa)=3026/T+5.814 (523 K≤ T ≤623 K) for hydriding and Igp (0.1 Mpa)=-3613/T+6.715 (523 K≤T ≤623 K) for dehydriding. The kinetic equation is [-ln(1 - α)]3/2 = kt and the apparent activation energy for thenucleation and growth-controlled hydrogen absorption and desorption were determined to be 64.3±2.31 kJ/(mol.H2)and 59.9±2.99 kJ/(moI.H2) respectively.

  19. Hydride interference on the determination of minor actinide isotopes by inductively coupled plasma mass spectrometry

    International Nuclear Information System (INIS)

    Hydrogen adducts of the major naturally occurring actinide isotopes 232Th and 238U were studied using an inductively coupled plasma mass spectrometer. The hydride:atomic ion ratios for both elements varied as a function of the parameters that were studied, i.e., nebulizer flow rate, solution uptake rate and desolvation conditions. When the instrument sensitivity for U and Th was optimized, 232ThH+:232Th+ was found to be (3.9±0.2) x 10-5 with pneumatic nebulization and (2.10±0.07) x 10-5 with ultrasonic nebulization. Under the same conditions, 238UH+:238U+ was found to be (3.2±0.2) x 10-5 and (1.8±0.1) x 10-5 using pneumatic and ultrasonic nebulization, respectively. Conditions that reduced hydrogen number density and/or increased plasma temperature decreased the hydride:atomic ion ratio. Such conditions are best if 233U and 239Pu are to be determined in the presence of 232Th and 238U. (Author)

  20. Production and characterization of thin film group IIIB, IVB and rare earth hydrides by reactive evaporation

    Energy Technology Data Exchange (ETDEWEB)

    Provo, James L., E-mail: jlprovo@verizon.net [Consultant, J.L. Provo Consulting, Trinity, Florida 34655-7179 (United States)

    2015-07-15

    A recent short history of reactive evaporation by D. M. Mattox [History Corner—A Short History of Reactive Evaporation, SVC Bulletin (Society of Vacuum Coaters, Spring 2014), p. 50–51] describes various methods for producing oxides, nitrides, carbides, and some compounds, but hydrides were not mentioned. A study was performed in the mid-1970s at the General Electric Company Neutron Devices Department in Largo, FL, by the author to study preparation of thin film hydrides using reactive evaporation and to determine their unique characteristics and properties. Films were produced of scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), and the rare earth praseodymium (Pr), neodymium (Nd), gadolinium (Gd), dysprosium (Dy), and erbium (Er) hydrides by hot crucible filament and electron beam evaporation in atmospheres of deuterium and tritium gases. All-metal vacuum systems were used and those used with tritium were dedicated for this processing. Thin film test samples 1000 nm thick were prepared on 1.27 cm diameter molybdenum disk substrates for each occluder (i.e., an element that can react with hydrogen to form a hydride) material. Loading characteristics as determined by gas-to-metal atomic ratios, oxidation characteristics as determined by argon–sputter Auger analysis, film structure as determined by scanning electron microscope analysis, and film stress properties as determined by a double resonator technique were used to define properties of interest. Results showed hydrogen-to-metal atomic ratios varied from 1.5 to 2.0 with near maximum loading for all but Pr and Nd occluders which correlated with the oxidation levels observed, with all occluder oxidation levels being variable due to vacuum system internal processing conditions and the materials used. Surface oxide levels varied from ∼80 Å to over 1000 Å. For most films studied, results showed that a maximum loading ratio of near 2.0 and a minimum surface oxide level of ∼80 Å could be

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

    Science.gov (United States)

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

    2007-03-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Karadjova, Irina B.; Petrov, Panayot K. [Faculty of Chemistry, University of Sofia, 1 James Bourchier Blvd., Sofia 1164 (Bulgaria); Serafimovski, Ivan [Food Institute, Faculty of Veterinary Medicine, Sts. Cyril and Methodius University, P.O. Box 95, MK-1000, Skopje (Macedonia, The Former Yugoslav Republic of); Stafilov, Trajce [Institute of Chemistry, Faculty of Science, Sts. Cyril and Methodius University, P.O. Box 162, MK-1000, Skopje (Macedonia, The Former Yugoslav Republic of); Tsalev, Dimiter L. [Faculty of Chemistry, University of Sofia, 1 James Bourchier Blvd., Sofia 1164 (Bulgaria)], E-mail: tsalev@chem.uni-sofia.bg

    2007-03-15

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

  3. 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

    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...

  4. SPECIATION OF SELENIUM(IV) AND SELENIUM(VI) USING COUPLED ION CHROMATOGRAPHY: HYDRIDE GENERATION ATOMIC ABSORPTION SPECTROMETRY

    Science.gov (United States)

    A simple method was developed to speciate inorganic selenium in the microgram per liter range using coupled ion chromatography-hydride generation atomic absorption spectrometry. Because of the differences in toxicity and adsorption behavior, determination of the redox states selenite, Se(IV), and s...

  5. Insight into the kinetics and thermodynamics of the hydride transfer reactions between quinones and lumiflavin: a density functional theory study.

    Science.gov (United States)

    Reinhardt, Clorice R; Jaglinski, Tanner C; Kastenschmidt, Ashly M; Song, Eun H; Gross, Adam K; Krause, Alyssa J; Gollmar, Jonathan M; Meise, Kristin J; Stenerson, Zachary S; Weibel, Tyler J; Dison, Andrew; Finnegan, Mackenzie R; Griesi, Daniel S; Heltne, Michael D; Hughes, Tom G; Hunt, Connor D; Jansen, Kayla A; Xiong, Adam H; Hati, Sanchita; Bhattacharyya, Sudeep

    2016-09-01

    The kinetics and equilibrium of the hydride transfer reaction between lumiflavin and a number of substituted quinones was studied using density functional theory. The impact of electron withdrawing/donating substituents on the redox potentials of quinones was studied. In addition, the role of these substituents on the kinetics of the hydride transfer reaction with lumiflavin was investigated in detail under the transition state (TS) theory assumption. The hydride transfer reactions were found to be more favorable for an electron-withdrawing substituent. The activation barrier exhibited a quadratic relationship with the driving force of these reactions as derived under the formalism of modified Marcus theory. The present study found a significant extent of electron delocalization in the TS that is stabilized by enhanced electrostatic, polarization, and exchange interactions. Analysis of geometry, bond-orders, and energetics revealed a predominant parallel (Leffler-Hammond) effect on the TS. Closer scrutiny reveals that electron-withdrawing substituents, although located on the acceptor ring, reduce the N-H bond order of the donor fragment in the precursor complex. Carried out in the gas-phase, this is the first ever report of a theoretical study of flavin's hydride transfer reactions with quinones, providing an unfiltered view of the electronic effect on the nuclear reorganization of donor-acceptor complexes. PMID:27491848

  6. Bepaling van arseen in grond m.b.v. atoomabsorptie spectrometrie in combinatie met een hydride systeem

    NARCIS (Netherlands)

    Driessen, A.C.M.; Moraal, J.C.; Werdmuller, G.A.; Veen, van der N.G.

    1982-01-01

    Het ontwikkelen van een snelle eenvoudige destruktiemethode voor de bepaling van totaal arseen in grond. Voor de bepaling van arseen in grond zijn een 10-tal destruktiemethoden onderzocht, waarbij de verkregen destruaten m.b.v. hydride-AAS bij 193.7 nm werden gemeten. Hierbij werd gebruik gemaakt va

  7. Effect of Cold Rolling on the Hydrogen Desorption Behavior of Binary Metal Hydride Powders under Microwave Irradiation

    Directory of Open Access Journals (Sweden)

    Ivaldete da Silva Dupim

    2015-10-01

    Full Text Available In this paper we report that cold rolling could drastically improve hydrogen desorption kinetics under microwave irradiation. Samples of metal hydride powders (TiH2, ZrH2, and MgH2 in as-received conditions and after cold rolling were microwave irradiated in a vacuum using a simple experimental setup. After irradiation, the samples were characterized by X-ray diffraction in other to evaluate the effectiveness of microwave heating. The diffraction patterns indicated that only MgH2 could be fully decomposed (dehydrided in the as received state. TiH2 was only partially decomposed while no decomposition was observed for ZrH2. However, cold rolling the hydride powders prior to microwave heating led to a significant improvement of hydride decomposition, resulting in the complete dehydriding of TiH2 and extensive dehydriding of ZrH2. These results clearly indicated the positive effects of cold rolling on the microwave assisted desorption of the investigated binary hydrides.

  8. Materials considerations in the design of a metal-hydride heat pump for an advanced extravehicular mobility unit

    Science.gov (United States)

    Liebert, B. E.

    1986-01-01

    A metal-hydride heat pump (HHP) has been proposed to provide an advanced regenerable nonventing thermal sink for the liquid-cooled garment worn during an extravehicular activity (EVA). The conceptual design indicates that there is a potential for significant advantages over the one presently being used by shuttle crew personnel as well as those that have been proposed for future use with the space station. Compared to other heat pump designs, a HHP offers the potential for extended use with no electrical power requirements during the EVA. In addition, a reliable, compact design is possible due to the absence of moving parts other than high-reliability check valves. Because there are many subtleties in the properties of metal hydrides for heat pump applications, it is essential that a prototype hydride heat pump be constructed with the selected materials before a committment is made for the final design. Particular care must be given to the evaporator heat exchanger worn by the astronaut since the performance of hydride heat pumps is generally heat transfer limited.

  9. Insight into the kinetics and thermodynamics of the hydride transfer reactions between quinones and lumiflavin: a density functional theory study.

    Science.gov (United States)

    Reinhardt, Clorice R; Jaglinski, Tanner C; Kastenschmidt, Ashly M; Song, Eun H; Gross, Adam K; Krause, Alyssa J; Gollmar, Jonathan M; Meise, Kristin J; Stenerson, Zachary S; Weibel, Tyler J; Dison, Andrew; Finnegan, Mackenzie R; Griesi, Daniel S; Heltne, Michael D; Hughes, Tom G; Hunt, Connor D; Jansen, Kayla A; Xiong, Adam H; Hati, Sanchita; Bhattacharyya, Sudeep

    2016-09-01

    The kinetics and equilibrium of the hydride transfer reaction between lumiflavin and a number of substituted quinones was studied using density functional theory. The impact of electron withdrawing/donating substituents on the redox potentials of quinones was studied. In addition, the role of these substituents on the kinetics of the hydride transfer reaction with lumiflavin was investigated in detail under the transition state (TS) theory assumption. The hydride transfer reactions were found to be more favorable for an electron-withdrawing substituent. The activation barrier exhibited a quadratic relationship with the driving force of these reactions as derived under the formalism of modified Marcus theory. The present study found a significant extent of electron delocalization in the TS that is stabilized by enhanced electrostatic, polarization, and exchange interactions. Analysis of geometry, bond-orders, and energetics revealed a predominant parallel (Leffler-Hammond) effect on the TS. Closer scrutiny reveals that electron-withdrawing substituents, although located on the acceptor ring, reduce the N-H bond order of the donor fragment in the precursor complex. Carried out in the gas-phase, this is the first ever report of a theoretical study of flavin's hydride transfer reactions with quinones, providing an unfiltered view of the electronic effect on the nuclear reorganization of donor-acceptor complexes.

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

    Energy Technology Data Exchange (ETDEWEB)

    Jason D. Hales; Veena Tikare

    2014-04-01

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

  11. Bed geometries, fueling strategies and optimization of heat exchanger designs in metal hydride storage systems for automotive applications: A review

    DEFF Research Database (Denmark)

    Mazzucco, Andrea; Dornheim, Martin; Sloth, Michael;

    2014-01-01

    given to metal hydride storage tanks for light duty vehicles, since this application is the most promising one for such storage materials and has been widely studied in the literature. Enhancing cooling/heating during hydrogen uptake and discharge has found to be essential to improve storage systems...

  12. Zirconium alloy oxidation and hydriding under irradiation: Review of Pacific Northwest Laboratories' test program results: Final report

    International Nuclear Information System (INIS)

    Radiation effects on zirconium alloy oxidation and hydriding were investigated in the Advanced Test Reactor (ATR) and Engineering Test Reactor (ETR). The investigations represent one of the largest data bases on oxidation and hydriding of zirconium alloys. Much of the data base has been published, but some results were unpublished when the federal programs terminated. Due to the renewed interest in zirconium alloy cladding behavior, the Electric Power Research Institute sponsored documentation of the unpublished results and a summary of principal results from the prior publications. The data base involves nine zirconium alloys; multiple metallurgical conditions; neutron flux levels from ∼1012 to 1.8 x 1014 n/cm2 .sec, > 1 MeV; fluence levels to 1.5 x 1022 n/cm2, > 1 MeV; oxygenated and low-oxygen coolants; in flux, out-of-flux, and out-of-reactor comparisons on identical specimens; transfer of specimens exposed in one loop water chemistry to another loop chemistry; dissimilar metal combinations; investigation of surface pretreatment effects. The loop results parallel in several respects oxidation and hydriding characteristics of water reactor fuel cladding and pressure tubes. The report summarizes results on the following areas; oxidation and hydriding trends under irradiation; localized phenomena; unusual oxidation effects; dissimilar metal effects; effects of fluoride contamination; metal density changes; deposition phenomena

  13. LDA or GGA? A combined experimental inelastic neutron scattering and ab initio lattice dynamics study of alkali metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Barrera, G.D. [ISIS Facility, Rutherford Appleton Laboratory, Chilton, Didcot, Oxon OX11 0QX (United Kingdom); Departamento de Quimica, Universidad Nacional de la Patagonia SJB, Ciudad Universitaria, 9005 Comodoro Rivadavia (Argentina); Colognesi, D. [Consiglio Nazionale delle Ricerche, Istituto dei Sistemi Complessi, via Madonna del Piano s.n.c., 50019 Sesto Fiorentino (Finland) (Italy); Mitchell, P.C.H. [School of Chemistry, University of Reading, RG6 6AD (United Kingdom); Ramirez-Cuesta, A.J. [ISIS Facility, Rutherford Appleton Laboratory, Chilton, Didcot, Oxon OX11 0QX (United Kingdom); School of Chemistry, University of Reading, RG6 6AD (United Kingdom)], E-mail: a.j.ramirez-cuesta@rl.ac.uk

    2005-10-31

    In a previous work, we carried out inelastic neutron scattering (INS) spectroscopy experiments and preliminary first principles calculations on alkali metal hydrides. The complete series of alkali metal hydrides, LiH, NaH, KH, RbH and CsH was measured in the high-resolution TOSCA INS spectrometer at ISIS. Here, we present the results of ab initio electronic structure calculations of the properties of the alkali metal hydrides using both the local density approximation (LDA) and the generalized gradient approximation (GGA), using the Perdew-Burke-Ernzerhof (PBE) parameterization. Properties calculated were lattice parameters, bulk moduli, dielectric constants, effective charges, electronic densities and inelastic neutron scattering (INS) spectra. We took advantage of the currently available computer power to use full lattice dynamics theory to calculate thermodynamic properties for these materials. For the alkali metal hydrides (LiH, NaH, KH, RbH and CsH) using lattice dynamics, we found that the INS spectra calculated using LDA agreed better with the experimental data than the spectra calculated using GGA. Both zero-point effects and thermal contributions to free energies had an important effect on INS and several thermodynamic properties.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-07-01

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

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

    KAUST Repository

    Werghi, Baraa

    2015-07-17

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

  16. Research the radiant character of hydride AlH2 free radical molecular spectrum

    International Nuclear Information System (INIS)

    This paper uses the calculated of vibration frequency, rotational constant and partition functions in previous paper, then puts the normal temperature calculated by moment squareRV2, which has no rotational transition, approximately as a constant and applied to high temperature, and lastly programs and computes the spectrum intensities and absorption coefficients of 001-000 and for hydride AlH2 free radical molecule at several temperatures. The results of previous paper show that the calculated values of total internal partition function agree with the datum obtained from Gauss calculations and fitted values. Such excellent agreement has made it feasible to calculate the spectrum radiation intensities and absorption coefficients at different temperatures. From the spectral figures at different temperatures, we find that they accord with the spectrum characteristic of asymmetric top molecules in some literature. This analysis has significance in measuring the high-temperature spectrum of radical molecules by experiment. (authors)

  17. Transition Spectrum Intensities and Absorption Coefficients of Hydride BH2 Free Radical Molecule

    International Nuclear Information System (INIS)

    We build a partition function model by product approximation first, then put the normal temperature calculated by moment square R2V, which has no rotational transition, approximately as a constant and applied to high temperature, and lastly program the compiler and compute the spectral line intensities and absorption coefficients of the 001-000 band for the hydride BH2 free radical molecule at several temperatures. The results show that the calculated values of total partition function agree with the data obtained from Gauss calculations and the fitted values by five factorial polynomials. Such excellent agreement has made it feasible to calculate the spectral line intensities and absorption coefficients at different temperatures. From the spectral figures at different temperatures, we find that they accord with the spectrum characteristic of asymmetric top molecules in some literature. This analysis has significance in measuring the high-temperature spectrum intensities of radical molecules by experiment. (atomic and molecular physics)

  18. The crystallization behaviour of sodium oxide and sodium hydride from liquid sodium

    International Nuclear Information System (INIS)

    Experiments are described in which electrochemical meters are used to follow crystallization and dissolution of sodium oxide and sodium hydride in a plugging meter. The technique enables precipitates to be identified unambiguously and allows the rates of precipitation to be related to solute supersaturation. Alternative theoretical models for crystal nucleation and growth are compared by fitting the kinetic data to published equations. The crystal growth of Na2O and NaH can be adequately described by a diffusion limited mechanism, though the growth of NaH may equally be limited by surface nucleation. Expressions are derived which enable the composition of co-precipitated deposits to be predicted. Calculations based on published heat and mass transfer equations suggest that in the cooled region of a cold trap, crystallization within the bulk flow is possible if there is no mesh to reduce concentration gradients. (author)

  19. Chemical vapour deposition of amorphous Ru(P) thin films from Ru trialkylphosphite hydride complexes.

    Science.gov (United States)

    McCarty, W Jeffrey; Yang, Xiaoping; DePue Anderson, Lauren J; Jones, Richard A

    2012-11-21

    The ruthenium phosphite hydride complexes H(2)Ru(P(OR)(3))(4) (R = Me (1), Et (2), (i)Pr (3)) were used as CVD precursors for the deposition of films of amorphous ruthenium-phosphorus alloys. The as-deposited films were X-ray amorphous and XPS analysis revealed that they were predominantly comprised of Ru and P in zero oxidation states. XPS analysis also showed the presence of small amounts of oxidized ruthenium and phosphorus. The composition of the films was found to depend on ligand chemistry as well as the deposition conditions. The use of H(2) as the carrier gas had the effect of increasing the relative concentrations of P and O for all films. Annealing films to 700 °C under vacuum produced films of polycrystalline hcp Ru while a flowing stream of H(2) resulted in polycrystalline hcp RuP. PMID:23018487

  20. High-Precision Selenium Isotope Analysis by Hydride Generation MC-ICP-MS: Environmental Applications

    Science.gov (United States)

    Schmidberger, S.; Simonetti, A.; Gariépy, C.

    2003-04-01

    The global cycle and the natural isotopic variation of Se in the lithosphere, biosphere, hydrosphere and atmosphere are currently little constrained. The study of Se isotope systematics by negative thermal ionization mass spectrometry (NTIMS) has documented large Se isotope variations up to 15 ppm in various natural samples (δ80Se/76Se; Johnson et al., 1999), indicating its important potential as a tracer in geological and biological processes. Recently, Se isotope measurements on sulfide deposits from hydrothermal systems were obtained using a Micromass IsoProbe multicollector inductively coupled plasma mass spectrometer coupled to a hydride generator (Rouxel et al. 2002). This technique allows for high-precision Se isotope analysis on small sample sizes (Marin, Y. Fouquet, (2002), Geochim. Cosmochim. Acta 66: 3191-3199

  1. FY 2016 Status Report: CIRFT Testing on Spent Nuclear Fuels and Hydride Reorientation Study

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jy-An John [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division; Wang, Hong [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division; Yan, Yong [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division; Bevard, Bruce B. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division; Scaglione, John M. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division

    2016-08-04

    This report provides a detailed description of the Cyclic Integrated Reversible-Bending Fatigue Tester (CIRFT) testing conducted on spent nuclear fuel (SNF) rods in FY 2016, including hydride reorientation test results. Contact-based measurement, or three-LVDT-based curvature measurement, of SNF rods has proven to be quite reliable in CIRFT testing. However, how the linear variable differential transformer (LVDT) head contacts the SNF rod may have a significant effect on the curvature measurement, depending on the magnitude and direction of rod curvature. To correct such contact/curvature issues, sensor spacing, defined as the amount of separation between the three LVDT probes, is a critical measurement that can be used to calculate rod curvature once the deflections are obtained.

  2. Development of high-capacity nickel-metal hydride batteries using superlattice hydrogen-absorbing alloys

    International Nuclear Information System (INIS)

    New R-Mg-Ni (R: rare earths) superlattice alloys with higher-capacity and higher-durability than the conventional Mm-Ni alloys with CaCu5 structure have been developed. The oxidation resistibility of the superlattice alloys has been improved by optimizing the alloy composition by such as substituting aluminum for nickel and optimizing the magnesium content in order to prolong the battery life. High-capacity nickel-metal hydride batteries for the retail market, the Ni-MH2500/900 series (AA size type 2500mAh, AAA size type 900mAh), have been developed and commercialized by using an improved superlattice alloy for negative electrode material. alized by using an improved superlattice alloy for negative electrode material. (author)

  3. Structure improvement and electrochemical studies of bipolar nickel metal hydride batteries for hybrid electric vehicles

    Institute of Scientific and Technical Information of China (English)

    DENG Chao; SHI Peng-fei

    2006-01-01

    Nickel metal hydride battery in bipolar design offers some advantages for its application as a power storage system for electric and hybrid vehicles. This paper deals with the structure design and electrochemical studies of bipolar Ni/MH batteries for hybrid vehicles. An improvement is applied in bipolar battery design,and such bipolar Ni/MH batteries with 5 sub-cells have been assembled and investigated. Testing results show that bipolar batteries with improved structure have better compression tolerance and cycle performance than conventional ones. In addition, the improved bipolar batteries display excellent large current discharge ability and high power density. As simulating working conditions for hybrid vehicles, the batteries show good stability during pulse cycles, which verifies the possibility of being used as a power storage device on hybrid vehicles.

  4. Effect of Overcharge on Electrochemical Performance of Sealed-Type Nickel/Metal Hydride Batteries

    Institute of Scientific and Technical Information of China (English)

    LI Li; WU Feng; CHEN Ren-jie; CHEN Shi

    2005-01-01

    The effects of overcharge on electrochemical performance of AA size sealed-type nickel/metal hydride(Ni/MH) batteries and its degradation mechanism were investigated. The results indicated that the relationship between the effects of different overcharge currents on the increasing velocity of inner pressure and the degradation velocity of cycle life and discharge voltage remains in almost direct proportion. After overcharge cycles, the positive electrode materials remain the original structure, but there occur some breaks because of the irreversible expand of crystal lattice. And the negative electrode alloy particles have inconspicuous pulverization, but are covered with lots of corrosive products and its main component is rare earth hydroxide or oxide. These are all the main reasons leading to the degradation behavior of the discharge capacity and cycle life of Ni/MH batteries.

  5. Silicon hydride nanocrystals as catalysts for proton production in water-organic liquid mixtures

    KAUST Repository

    Chaieb, Sahraoui

    2014-08-05

    Embodiments of the present methods may be used to produce energy in the form of an electrical current from water without the use of fossil fuel. Silicon hydride is very easy to make. This procedure in conjunction with an enzyme to produce hydrogen gas for fuel cells and other small devices. In fuel cells the production of protons may be bypassed, and an oxidant such as permanganate or oxygen from air may be used to drive the fuel cells. In such an embodiment, an intermediate reaction may not be needed to produce protons. In one embodiment, membrane-less laminar flow fuel cells with an external grid for oxygen supply from the air may be used.

  6. Quantum Simulation of Helium Hydride Cation in a Solid-State Spin Register.

    Science.gov (United States)

    Wang, Ya; Dolde, Florian; Biamonte, Jacob; Babbush, Ryan; Bergholm, Ville; Yang, Sen; Jakobi, Ingmar; Neumann, Philipp; Aspuru-Guzik, Alán; Whitfield, James D; Wrachtrup, Jörg

    2015-08-25

    Ab initio computation of molecular properties is one of the most promising applications of quantum computing. While this problem is widely believed to be intractable for classical computers, efficient quantum algorithms exist which have the potential to vastly accelerate research throughput in fields ranging from material science to drug discovery. Using a solid-state quantum register realized in a nitrogen-vacancy (NV) defect in diamond, we compute the bond dissociation curve of the minimal basis helium hydride cation, HeH(+). Moreover, we report an energy uncertainty (given our model basis) of the order of 10(-14) hartree, which is 10 orders of magnitude below the desired chemical precision. As NV centers in diamond provide a robust and straightforward platform for quantum information processing, our work provides an important step toward a fully scalable solid-state implementation of a quantum chemistry simulator. PMID:25905564

  7. Properties of GaN on different polarity buffer layers by hydride vapour phase epitaxy

    Institute of Scientific and Technical Information of China (English)

    Qiu Kai; Zhong Fei; Li Xin-Hua; Yin Zhi-Jun; Ji Chang-Jian; Han Qi-Feng; Chen Jia-Rong; Cao Xian-Cun; Wang Yu-Qi

    2007-01-01

    This paper reports on N-, mixed-, and Ga-polarity buffer layers are grown by molecular beam epitaxy (MBE) on sapphire (0001) substrates, with the GaN thicker films grown on the buffer layer with different polarity by hydride vapour epitaxy technique (HVPE). The surface morphology, structural and optical properties of these HVPF-GaN epilayers are characterized by wet chemical etching, scanning electron microscope, x-ray diffraction, and photoluminescence spectrum respectively. It finds that the N-polarity film is unstable against the higher growth temperature and wet chemical etching,while that of GaN polarity one is stable. The results indicate that the crystalline quality of HVPE-GaN epilayers depends on the polarity of buffer layers.

  8. Arsenic Speciation of Waters from the Aegean Region, Turkey by Hydride Generation: Atomic Absorption Spectrometry.

    Science.gov (United States)

    Çiftçi, Tülin Deniz; Henden, Emur

    2016-08-01

    Arsenic in drinking water is a serious problem for human health. Since the toxicity of arsenic species As(III) and As(V) is different, it is important to determine the concentrations separately. Therefore, it is necessary to develop an accurate and sensitive method for the speciation of arsenic. It was intended with this work to determine the concentrations of arsenic species in water samples collected from Izmir, Manisa and nearby areas. A batch type hydride generation atomic absorption spectrometer was used. As(V) gave no signal under the optimal measurement conditions of As(III). A certified reference drinking water was analyzed by the method and the results showed excellent agreement with the reported values. The procedure was applied to 34 water samples. Eleven tap water, two spring water, 19 artesian well water and two thermal water samples were analyzed under the optimal conditions. PMID:27236436

  9. Dielectric barrier discharge plasma atomizer for hydride generation atomic absorption spectrometry—Performance evaluation for selenium

    International Nuclear Information System (INIS)

    Atomization of selenium hydride in a quartz dielectric barrier discharge (DBD) atomizer was optimized and its performance was compared to that of the externally heated quartz multiatomizer. Argon was found as the best DBD discharge gas employing a flow rate of 75 ml min−1 Ar while the DBD power was optimized at 14 W. The detection limits reached 0.24 ng ml−1 Se in the DBD and 0.15 ng ml−1 Se in the multiatomizer. The tolerance of DBD to interferences is even better than with the multiatomizer. - Highlights: • SeH2 atomization in a dielectric barrier discharge (DBD) was optimized for AAS. • Atomizer performance was compared for DBD and externally heated quartz atomizer. • Detection limits were quantified and interferences were studied in both atomizers. • Atomization efficiency in the DBD was estimated

  10. RF sputtering for controlling dihydride and monohydride bond densities in amorphous silicon hydride

    Science.gov (United States)

    Jeffery, F.R.; Shanks, H.R.

    1980-08-26

    A process is described for controlling the dihydride and monohydride bond densities in hydrogenated amorphous silicone produced by reactive rf sputtering of an amorphous silicon target. There is provided a chamber with an amorphous silicon target and a substrate therein with the substrate and the target positioned such that when rf power is applied to the target the substrate is in contact with the sputtering plasma produced thereby. Hydrogen and argon are fed to the chamber and the pressure is reduced in the chamber to a value sufficient to maintain a sputtering plasma therein, and then rf power is applied to the silicon target to provide a power density in the range of from about 7 watts per square inch to about 22 watts per square inch to sputter an amorphous solicone hydride onto the substrate, the dihydride bond density decreasing with an increase in the rf power density. Substantially pure monohydride films may be produced.

  11. Synthesis of Tetrahydroquinoline Derivatives via Oxidation and 1,5-Hydride Transfer/Cyclization Cascade

    Energy Technology Data Exchange (ETDEWEB)

    Suh, Chang Won; Jeong, Hyun Jung; Kim, Dae Young [Soonchunhyang University, Asan (Korea, Republic of)

    2015-01-15

    One-pot cascade reactions are useful synthetic transformations because they allow efficient construction of complex molecules. Such protocols can not only save operation time and cost but also minimize waste generation with elimination of tedious isolation procedures for each reaction. Given these advantages, much effort has been devoted to the development of new cascade reactions and the conversion of already existing multistep syntheses into the one-pot procedures. Recently, the oxidative iminium activation was reported by several research groups. This strategy involves the oxidation of an allylic alcohol and the subsequent secondary aminecatalyzed iminium reactions. We have presented the first example of an oxidation and organo catalytic hydride transfer/ring closure reaction cascade. The synthetically useful ring-fused tetrahydroquinoline derivatives were obtained in high yields and diastereo selectivities. Further investigations for the asymmetric version of this oxidation and organocatalytic internal redox reaction csacade are under way.

  12. Different failure modes for V-containing and V-free AB2 metal hydride alloys

    Science.gov (United States)

    Young, K.; Wong, D. F.; Yasuoka, S.; Ishida, J.; Nei, J.; Koch, J.

    2014-04-01

    Failure modes of a V-containing and a V-free AB2 Laves phase-based metal hydride alloy were studied by the combination of X-ray diffractometer, scanning electron microscope, X-ray energy dispersive spectroscopy, inductively coupled plasma, Soxhlet extraction, and magnetic susceptibility measurement. Cells with the V-containing alloy exhibited less capacity degradation up until venting occurred in the cells, after which the capacity rapidly degraded. Cells with the V-free alloy remained linear in capacity degradation throughout the cycle life test. The failure mechanism for the V-containing alloy is related to the formation of an oxide layer that penetrates deeper into the alloy particles due to high V leaching and impedes gas recombination, while the failure mechanism for the V-free alloy is related to the continuous pulverization of the main AB2 phase.

  13. Photorechargeable Properties of Metal Hydride-SrTiO3 Electrode

    Institute of Scientific and Technical Information of China (English)

    Wen Kui ZHANG; Xi Li TONG; Hui HUANG; Yong Ping GAN; Na HUANG

    2005-01-01

    A photosensitive metal hydride electrode was prepared by modification with perovskite-type SrTiO3 photocatalyst. The photorechargeable properties of the prepared electrodes were investigated by using electrochemical cyclic voltammetry and EIS measurements. The results showed that the modified electrode exhibited the obvious photorechargeable properties. The reduction current increased remarkably under the xeon light irradiation compared with the unmodified electrode. During the photocharging process, the potential of the modified electrode shifted quickly to negative direction and a potential plateau of about -0.90V (vs. Hg/HgO) occurred at the end of light irradiation. The corresponding discharge capacity of the electrode was about 5.4mAh/g.

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

    DEFF Research Database (Denmark)

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

    2016-01-01

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

  15. A titanium hydride gun for plasma injection into the T2-reversed field pinch device

    Science.gov (United States)

    Voronin, A. V.; Hellblom, K. G.

    1999-02-01

    A study of a plasma gun (modified Bostic type) with titanium hydride electrodes has been carried out. The total number of released hydrogen atoms was in the range 1016-1018 and the maximum plasma flow velocity was 2.5×105 m s-1. The ion density near the gun edge reached 1.8×1020 m-3 and the electron temperature was around 40 eV as estimated from probe measurements. No species other than hydrogen or titanium were seen in the plasma line radiation. The plasma injector was successfully used for gas pre-ionization in the Extrap T2 reversed-field pinch device (ohmic heating toroidal experiment (OHTE)).

  16. Luminescence transients in highly excited GaN grown by hydride vapor-phase epitaxy

    Energy Technology Data Exchange (ETDEWEB)

    Jursenas, S.; Miasojedovas, S.; Kurilcik, G.; Zukauskas, A. [Institute of Materials Science and Applied Research, Vilnius University, Sauletekio al. 9-III, LT-2040 Vilnius (Lithuania); Hageman, P.R. [University of Nijmegen, Fac. of Science, Dept. of Exp. Solid State Physics III, Toernooiveld 1, 6525 ED Nijmegen (Netherlands)

    2004-01-01

    Luminescence transients has been studied in GaN grown by hydride vapor-phase epitaxy (HVPE) under intense photoexcitation conditions. The HVPE grown GaN layer exhibited luminescence decay time of 205 ps, that implies the room-temperature free-carrier lifetime of 420 ps. The obtained carrier lifetime of HVPE-grown GaN is significantly higher that the typical values of carrier lifetime measured for GaN heterolayers grown by metalorganic chemical vapor deposition, what suggests high potential of HVPE growth technique for light-emitting diode and blue laser applications. (copyright 2004 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  17. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Tang Xia [United Technologies Research Center, 411 Silver Lane, East Hartford, CT 06108 (United States)], E-mail: tangx@utrc.utc.com; Opalka, Susanne M.; Laube, Bruce L. [United Technologies Research Center, 411 Silver Lane, East Hartford, CT 06108 (United States); Wu Fengjung; Strickler, Jamie R. [Albemarle Corporation, Gulf States Road, Baton Rouge, LA 70805 (United States); Anton, Donald L. [Savannah River National Laboratory, 227 Gateway Dr., Aiken, SC 29808 (United States)

    2007-10-31

    Lightweight complex hydrides have attracted attention for their high storage hydrogen capacity. NaAlH{sub 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{sub 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.

  19. Dielectric barrier discharge plasma atomizer for hydride generation atomic absorption spectrometry—Performance evaluation for selenium

    Energy Technology Data Exchange (ETDEWEB)

    Duben, Ondřej [Institute of Analytical Chemistry of the CAS, v.v.i., Veveří 97, CZ-602 00 Brno (Czech Republic); Faculty of Science, Department of Analytical Chemistry, Charles University in Prague, Hlavova 8, Prague, CZ 128 43 Czech Republic (Czech Republic); Boušek, Jaroslav [Faculty of Electrical Engineering and Communications, Brno University of Technology, Technická 1058/10, 61600 Brno (Czech Republic); Dědina, Jiří [Institute of Analytical Chemistry of the CAS, v.v.i., Veveří 97, CZ-602 00 Brno (Czech Republic); Kratzer, Jan, E-mail: jkratzer@biomed.cas.cz [Institute of Analytical Chemistry of the CAS, v.v.i., Veveří 97, CZ-602 00 Brno (Czech Republic)

    2015-09-01

    Atomization of selenium hydride in a quartz dielectric barrier discharge (DBD) atomizer was optimized and its performance was compared to that of the externally heated quartz multiatomizer. Argon was found as the best DBD discharge gas employing a flow rate of 75 ml min{sup −1} Ar while the DBD power was optimized at 14 W. The detection limits reached 0.24 ng ml{sup −1} Se in the DBD and 0.15 ng ml{sup −1} Se in the multiatomizer. The tolerance of DBD to interferences is even better than with the multiatomizer. - Highlights: • SeH{sub 2} atomization in a dielectric barrier discharge (DBD) was optimized for AAS. • Atomizer performance was compared for DBD and externally heated quartz atomizer. • Detection limits were quantified and interferences were studied in both atomizers. • Atomization efficiency in the DBD was estimated.

  20. Control of PDMS crosslinking by encapsulating a hydride crosslinker in a PMMA microcapsule

    DEFF Research Database (Denmark)

    Ma, Baoguang; Hansen, Jens Henrik; Hvilsted, Søren;

    2014-01-01

    crosslinker in a PMMA shell. Microcapsules are mixed with vinyl-terminated PDMS to create a gelation system, which allows for storage at 50 °C, without premature gelation, and in addition allows for extensive crosslinking reaction at 120 °C. Both visual observations and rheological studies show that a robust...... PDMS elastomer is obtained upon heating the gelation system. Furthermore, the influence of stoichiometric imbalance on the equilibrium storage modulus of the PDMS network is investigated, by employing different amounts of microcapsules in vinyl-terminated PDMS. It has been found that adding...... microcapsules increases the equilibrium storage modulus of the PDMS elastomer until the diffusion of the hydride crosslinker is constricted. An optimum amount of crosslinker used in the control crosslinking reaction has also been found. However, compared to the pure PDMS elastomer, the modulus of the PDMS...

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

    Institute of Scientific and Technical Information of China (English)

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

    2013-01-01

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

  2. Surface Modification for Metal Hydride Electrode of Ni/MH Battery

    Institute of Scientific and Technical Information of China (English)

    YANG Kai; WU Feng; LI Li; CHEN Shi

    2005-01-01

    A novel method was applied to the surface modification of the metal hydride (MH) electrode of the Ni/MH battery. The electrode was plated with a thin silver film by using plasma technology and its effect on the performance of the Ni/MH battery was examined. Charge-discharge test proved that the battery with modified electrode exhibits a better high-rate dischargeability and chargeability than the battery with untreated electrode. The battery with modified electrode exhibits satisfactory durability. After 500 cycles, the capacities of the batteries with modified and unmodified electrode are 90.1% and 82.3% of their original capacities. The inner pressure test shows that the battery with modified electrode displays a much lower inner gas pressure on charging. The experimental results demonstrate that this method is an effective way for the surface modification of the electrode of the Ni/MH battery.

  3. Mg-Ni THIN FILM-A POTENTIAL NEGATIVE ELECTRODE FOR NIKEL-METAL HYDRIDE BATTERY

    Institute of Scientific and Technical Information of China (English)

    L.Z. Ouyang; C.Y. Chung; M.Q. Zeng; H. Wang; M. Zhu

    2003-01-01

    Mg-Ni thin films for nickel-metal hydride (Ni-MH) battery negative electrode were prepared on three different substrates by using magnetron sputtering with compacted Ni and Mg mixture powder. The microstructure of Mg-Ni thin films deposited on the glass and the Ni foil substrate respectively was studied by X-ray diffraction (XRD)and scanning electron microscopy (SEM). The results show that the Mg-Ni thin films were in amorphous structure and the composition of the thin film was homogeneous.Electrochemical measurement show the discharge capacity of the thin film negative electrode deposited on the foam Ni substrate was 234.8mAh/g in 6M alkaline electrolyte and the internal resistance was much lower than that of the electrode prepared by the ball-milled powder during the charge-discharge cycle.

  4. Metal Hydrides, MOFs, and Carbon Composites as Space Radiation Shielding Mitigators

    Science.gov (United States)

    Atwell, William; Rojdev, Kristina; Liang, Daniel; Hill, Matthew

    2014-01-01

    Recently, metal hydrides and MOFs (Metal-Organic Framework/microporous organic polymer composites - for their hydrogen and methane storage capabilities) have been studied with applications in fuel cell technology. We have investigated a dual-use of these materials and carbon composites (CNT-HDPE) to include space radiation shielding mitigation. In this paper we present the results of a detailed study where we have analyzed 64 materials. We used the Band fit spectra for the combined 19-24 October 1989 solar proton events as the input source term radiation environment. These computational analyses were performed with the NASA high energy particle transport/dose code HZETRN. Through this analysis we have identified several of the materials that have excellent radiation shielding properties and the details of this analysis will be discussed further in the paper.

  5. Electrical, optical, and structural properties of GaN films prepared by hydride vapor phase epitaxy

    International Nuclear Information System (INIS)

    Highlights: • GaN films are prepared by hydride vapor phase epitaxy (HVPE). • Residual donors and deep traps show a minimum density versus growth temperature. • This minimum is located close to the HVPE growth temperature of 950 °C. • Good crystalline GaN with residual donor density < 1016 cm−3 can be grown at 950 °C. - Abstract: Two sets of undoped GaN films with the thickness of 10–20 μm were prepared by hydride vapor phase epitaxy (HVPE) and characterized by capacitance–voltage (C–V) profiling, microcathodoluminescence (MCL) spectra measurements, MCL imaging, electron beam induced current (EBIC) imaging, EBIC dependence on accelerating voltage, deep levels transient spectroscopy, high resolution X-ray diffraction measurements. The difference in growth conditions was mainly related to the lower (850 °C, group 1) or higher (950 °C, group 2) growth temperature. Both groups of samples showed similar crystalline quality with the dislocation density close to 108 cm−2, but very different electrical and optical properties. In group 1 samples the residual donors concentration was ∼1017 cm−3 or higher, the MCL spectra were dominated by the band-edge luminescence, and the diffusion length of charge carriers was close to 0.1 μm. Group 2 samples had a 2–4.5 μm thick highly resistive layer on top, for which MCL spectra were determined by green, yellow and red defect bands, and the diffusion length was 1.5 times higher than in group 1. We also present brief results of growth at the “standard” HVPE growth temperature of 1050 °C that show the presence of a minimum in the net donor concentration and deep traps density as a function of the growth temperature. Possible reasons for the observed results are discussed in terms of the electrical compensation of residual donors by deep traps

  6. Anisotropic Azimuthal Power and Temperature distribution on FuelRod. Impact on Hydride Distribution

    Energy Technology Data Exchange (ETDEWEB)

    Motta, Arthur [Pennsylvania State Univ., State College, PA (United States); Ivanov, Kostadin [Pennsylvania State Univ., State College, PA (United States); Arramova, Maria [Pennsylvania State Univ., State College, PA (United States); Hales, Jason [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2015-04-29

    The degradation of the zirconium cladding may limit nuclear fuel performance. In the high temperature environment of a reactor, the zirconium in the cladding corrodes, releasing hydrogen in the process. Some of this hydrogen is absorbed by the cladding in a highly inhomogeneous manner. The distribution of the absorbed hydrogen is extremely sensitive to temperature and stress concentration gradients. The absorbed hydrogen tends to concentrate near lower temperatures. This hydrogen absorption and hydride formation can cause cladding failure. This project set out to improve the hydrogen distribution prediction capabilities of the BISON fuel performance code. The project was split into two primary sections, first was the use of a high fidelity multi-physics coupling to accurately predict temperature gradients as a function of r, θ , and z, and the second was to use experimental data to create an analytical hydrogen precipitation model. The Penn State version of thermal hydraulics code COBRA-TF (CTF) was successfully coupled to the DeCART neutronics code. This coupled system was verified by testing and validated by comparison to FRAPCON data. The hydrogen diffusion and precipitation experiments successfully calculated the heat of transport and precipitation rate constant values to be used within the hydrogen model in BISON. These values can only be determined experimentally. These values were successfully implemented in precipitation, diffusion and dissolution kernels that were implemented in the BISON code. The coupled output was fed into BISON models and the hydrogen and hydride distributions behaved as expected. Simulations were conducted in the radial, axial and azimuthal directions to showcase the full capabilities of the hydrogen model.

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

    Science.gov (United States)

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

    2016-02-01

    After the Fukushima disaster, power generation from nuclear power plants in Japan was completely stopped and old coal-based power plants were re-commissioned to compensate for the decrease in power generation capacity. Although coal is a relatively inexpensive fuel for power generation, it contains high levels (mgkg(-1)) of selenium, which could contaminate the wastewater from thermal power plants. In this work, an automated selenium monitoring system was developed based on sequential hydride generation and chemiluminescence detection. This method could be applied to control of wastewater contamination. In this method, selenium is vaporized as H2Se, which reacts with ozone to produce chemiluminescence. However, interference from arsenic is of concern because the ozone-induced chemiluminescence intensity of H2Se is much lower than that of AsH3. This problem was successfully addressed by vaporizing arsenic and selenium individually in a sequential procedure using a syringe pump equipped with an eight-port selection valve and hot and cold reactors. Oxidative decomposition of organoselenium compounds and pre-reduction of the selenium were performed in the hot reactor, and vapor generation of arsenic and selenium were performed separately in the cold reactor. Sample transfers between the reactors were carried out by a pneumatic air operation by switching with three-way solenoid valves. The detection limit for selenium was 0.008 mg L(-1) and calibration curve was linear up to 1.0 mg L(-1), which provided suitable performance for controlling selenium in wastewater to around the allowable limit (0.1 mg L(-1)). This system consumes few chemicals and is stable for more than a month without any maintenance. Wastewater samples from thermal power plants were collected, and data obtained by the proposed method were compared with those from batchwise water treatment followed by hydride generation-atomic fluorescence spectrometry. PMID:26653491

  8. Reduced enthalpy of metal hydride formation for Mg-Ti nanocomposites produced by spark discharge generation.

    Science.gov (United States)

    Anastasopol, Anca; Pfeiffer, Tobias V; Middelkoop, Joost; Lafont, Ugo; Canales-Perez, Roger J; Schmidt-Ott, Andreas; Mulder, Fokko M; Eijt, Stephan W H

    2013-05-29

    Spark discharge generation was used to synthesize Mg-Ti nanocomposites consisting primarily of a metastable body-centered-cubic (bcc) alloy of Mg and Ti. The bcc Mg-Ti alloy transformed upon hydrogenation into the face-centered-cubic fluorite Mg1-yTiyHx phase with favorable hydrogen storage properties. Both metal and metal hydride nanocomposites showed a fractal-like porous morphology, with a primary particle size of 10-20 nm. The metal content of 70 atom % (at %) Mg and 30 at % Ti, consistently determined by XRD, TEM-EDS, and ICP-OES, was distributed uniformly across the as-prepared sample. Pressure-composition isotherms for the Mg-Ti-H nanocomposites revealed large differences in the thermodynamics relative to bulk MgH2, with a much less negative enthalpy of formation of the hydride as small as -45 ± 3 kJ/molH2 as deduced from van't Hoff plots. The plateau pressures of hydrogenation were substantially higher than those for bulk MgH2 in the low temperature range from 150 to 250 °C. The reaction entropy was simultaneously reduced to values down to 84 ± 5 J/K mol H2, following a linear relationship between the enthalpy and entropy. Plausible mechanisms for the modified thermodynamics are discussed, including the effect of lattice strains, the presence of interfaces and hydrogen vacancies, and the formation of excess free volume due to local deformations. These mechanisms all rely on the finely interdispersed nanocomposite character of the samples which is maintained by grain refinement.

  9. NMR study of hydrogen diffusion in metal hydrides containing paramagnetic impurities

    International Nuclear Information System (INIS)

    The pulsed NMR of hydrogen nuclei in LaH/sub x/ and YH/sub x/ with and without paramagnetic impurities (Ce, Nd, Gd, Dy, Er) was studied. Measurements of proton T1 were carried out in the temperature range from 77K to 800K at a resonance frequencey of 40MHz. The data for both pure laH/sub x/ (1.8 less than or equal to x less than or equal to 2.46) and YH/sub x/ (1.81 less than or equal to x less than or equal to 2.03) show unambiguously that the hydrogen diffusion rate increases with increasing hydrogen content. It is concluded that increased occupancy of the octahedral sublattice causes the potential wells at octahedral and tetrahedral sites to become shallower and lowers the energy barrier to motion between the two sublattices. For systems with controlled dilute paramagnetic impurities, an additional spin-lattice relaxation process was found and appears to be essentially due to the dipolar coupling between impurity and proton moments. At low temperatures, protons far from the relaxation center are relaxed by the mechanism of spin diffusion. At higher temperatures, hydrogen diffusion becomes more rapid than spin diffusion and takes over as the mechanism for transporting distant spins to the relaxation center. This study shows that the impurity induced relaxation rate is very sensitive to the magnetic moment and relaxation rate of the impurity ion, as well as depending on the host hydride composition. Since various ions behave so differently, it is dangerous to generalize as to what effects on the proton T1 may be present in specific hydrides where the actual impurity content is unknown. Consequently, serious errors in deduced diffusion and electronic structure parameters may be made unless effects of impurities are recognized and allowed for

  10. Molecular Line Lists for Scandium and Titanium Hydride Using the DUO Program

    Science.gov (United States)

    Lodi, Lorenzo; Yurchenko, Sergei N.; Tennyson, Jonathan

    2015-06-01

    Transition-metal-containing (TMC) molecules often have very complex electronic spectra because of their large number of low-lying, interacting electronic states, of the large multi-reference character of the electronic states and of the large magnitude of spin-orbit and relativistic effects. As a result, fully ab initio calculations of line positions and intensities of TMC molecules have an accuracy which is considerably worse than the one usually achievable for molecules made up by main-group atoms only. In this presentation we report on new theoretical line lists for scandium hydride ScH and titanium hydride TiH. Scandium and titanium are the lightest transition metal atoms and by virtue of their small number of valence electrons are amenable to high-level electronic-structure treatments and serve as ideal benchmark systems. We report for both systems energy curves, dipole curves and various coupling curves (including spin-orbit) characterising their electronic spectra up to about 20 000 cm-1. Curves were obtained using Internally-Contracted Multi Reference Configuration Interaction (IC-MRCI) as implemented in the quantum chemistry package MOLPRO. The curves where used for the solution of the coupled-surface ro-vibronic problem using the in-house program DUO. DUO is a newly-developed, general program for the spectroscopy of diatomic molecules and its main functionality will be described. The resulting line lists for ScH and TiH are made available as part of the Exomol project. L. Lodi, S. N. Yurchenko and J. Tennyson, Mol. Phys. (Handy special issue) in press. S. N. Yurchenko, L. Lodi, J. Tennyson and A. V. Stolyarov, Computer Phys. Comms., to be submitted.

  11. Speciation analysis of arsenic in biological matrices by automated hydride generation-cryotrapping-atomic absorption spectrometry with multiple microflame quartz tube atomizer (multiatomizer).

    Science.gov (United States)

    This paper describes an automated system for the oxidation state specific speciation of inorganic and methylated arsenicals by selective hydride generation - cryotrapping- gas chromatography - atomic absorption spectrometry with the multiatomizer. The corresponding arsines are ge...

  12. DETERMINATION OF TRACE AMOUNTS OF SELENIUM IN CORN, LETTUCE, POTATOES, SOYBEANS, AND WHEAT BY HYDRIDE GENERATION/CONDENSATION AND FLAME ATOMIC ABSORPTION SPECTROMETRY

    Science.gov (United States)

    Because of the nutritional and toxicological significance of low selenium concentrations in agricultural crops, a procedure utilizing wet digestion followed by hydride generation/condensation-flame atomic absorption was developed for the routine analysis of selenium in different ...

  13. Mound Laboratory activities in chemical and physical research: July--December 1976. [Isotope separation; metal hydride research, separation chemistry and separation research

    Energy Technology Data Exchange (ETDEWEB)

    1977-05-04

    The status of the following programs is reported: isotope separation of carbon, argon, helium, krypton, neon, xenon, oxygen, and sulfur; metal hydride research; separation chemistry; and separation research. (LK)

  14. Study of hydrogen diffusion in amorphous and crystalline hydrides of the alloy Zr2Ni by gamma-gamma perturbed angular correlations of 181Ta

    International Nuclear Information System (INIS)

    The diffusion of hydrogen in crystalline hydrides Zr2NiHx (x = 2.1, 3 and 4.8) and amorphous hydrides of Zr2Ni with x = 2.5 and 4.5, has been studied by Perturbed Angular Correlation spectroscopy using 181Ta as a probe in substitution for zirconium. The quadrupole relaxation of the 181Ta spins produced by hydrogen motions was observed between 170 K and 470 K. The activation energy and pre-exponential frequency factors were deduced from the temperature dependence of the quadrupole relaxation constant in both crystalline and amorphous hydrides. In crystalline hydrides our results are consistent with those previously reported from 1H NMR experiments. Combining the PAC data with the results of neutron diffraction experiments performed on crystalline deuterides, we are able to propose a mechanism for hydrogen jumps in these hydrides using a single geometrical model. In the amorphous hydrides our PAC results are consistent with the existence of a short-range ordering or microsegregation induced by the hydrogen loading process in the amorphous lattice. However, our data do not indicate the existence of broad distributions of the activation energy for hydrogen jumps

  15. A model to describe the mechanical behavior and the ductile failure of hydrided Zircaloy-4 fuel claddings between 25 °C and 480 °C

    Science.gov (United States)

    Le Saux, M.; Besson, J.; Carassou, S.

    2015-11-01

    A model is proposed to describe the mechanical behavior and the ductile failure at 25, 350 and 480 °C of Zircaloy-4 cladding tubes, as-received and hydrided up to 1200 wt. ppm (circumferential hydrides). The model is based on the Gurson-Tvergaard-Needleman model extended to account for plastic anisotropy and viscoplasticity. The model considers damage nucleation by both hydride cracking and debonding of the interface between the Laves phase precipitates and the matrix. The damage nucleation rate due to hydride cracking is directly deduced from quantitative microstructural observations. The other model parameters are identified from several experimental tests. Finite element simulations of axial tension, hoop tension, expansion due to compression and hoop plane strain tension experiments are performed to assess the model prediction capability. The calibrated model satisfactorily reproduces the effects of hydrogen and temperature on both the viscoplastic and the failure properties of the material. The results suggest that damage is anisotropic and influenced by the stress state for the non-hydrided or moderately hydrided material and becomes more isotropic for high hydrogen contents.

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

    Science.gov (United States)

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

    2010-02-11

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

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

    Science.gov (United States)

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

    2009-02-01

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

  18. Scattering influences in quantitative fission neutron radiography for the in situ analysis of hydrogen distribution in metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Börries, S., E-mail: stefan.boerries@hzg.de [Helmholtz-Zentrum Geesthacht, Centre for Materials and Coastal Research, Max-Planck-Strasse 1, D-21502 Geesthacht (Germany); Metz, O.; Pranzas, P.K. [Helmholtz-Zentrum Geesthacht, Centre for Materials and Coastal Research, Max-Planck-Strasse 1, D-21502 Geesthacht (Germany); Bücherl, T. [ZTWB Radiochemie München (RCM), Technische Universität München (TUM), Walther-Meissner-Str. 3, D-85748 Garching (Germany); Söllradl, S. [Forschungs-Neutronenquelle Heinz Maier-Leibnitz (FRMII), Technische Universität München (TUM), Lichtenbergstr. 1, D-85748 Garching (Germany); Dornheim, M.; Klassen, T.; Schreyer, A. [Helmholtz-Zentrum Geesthacht, Centre for Materials and Coastal Research, Max-Planck-Strasse 1, D-21502 Geesthacht (Germany)

    2015-10-11

    In situ neutron radiography allows for the time-resolved study of hydrogen distribution in metal hydrides. However, for a precise quantitative investigation of a time-dependent hydrogen content within a host material, an exact knowledge of the corresponding attenuation coefficient is necessary. Additionally, the effect of scattering has to be considered as it is known to violate Beer's law, which is used to determine the amount of hydrogen from a measured intensity distribution. Within this study, we used a metal hydride inside two different hydrogen storage tanks as host systems, consisting of steel and aluminum. The neutron beam attenuation by hydrogen was investigated in these two different setups during the hydrogen absorption process. A linear correlation to the amount of absorbed hydrogen was found, allowing for a readily quantitative investigation. Further, an analysis of scattering contributions on the measured intensity distributions was performed and is described in detail.

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

    CERN Document Server

    Widom, A; Larsen, L

    2012-01-01

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

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

    Directory of Open Access Journals (Sweden)

    Mark R.StJ. Foreman

    2016-12-01

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

  1. Hydride generation and condensation flame atomic absorption spectroscopic determination of antimony in raw coffee beans and processed coffee.

    Science.gov (United States)

    Kuennen, R W; Hahn, M H; Fricke, F L; Wolnik, K A

    1982-09-01

    A method was developed for determining Sb at nanogram per gram levels in raw coffee beans and processed coffee. The procedure uses either total acid digestion or extraction with 6M HCl followed by hydride generation/condensation with subsequent revolatilization of stibine (SbH3) and detection by flame atomic absorption spectroscopy. The lowest quantifiable level, based on a 2 g (dry weight) sample, is 2 ng Sb/g. The results of recoveries on spiked samples, precision studies on composited coffee samples, and the analysis of National Bureau of Standards Standard Reference Materials demonstrate the reliability and accuracy of the procedure. Sb concentrations in coffee samples were verified by neutron activation analysis and inductively coupled plasma atomic emission spectroscopy. Advantages of the method compared with the AOAC colorimetric procedure and hydride generation without condensation are discussed. PMID:7130087

  2. Scattering influences in quantitative fission neutron radiography for the in situ analysis of hydrogen distribution in metal hydrides

    International Nuclear Information System (INIS)

    In situ neutron radiography allows for the time-resolved study of hydrogen distribution in metal hydrides. However, for a precise quantitative investigation of a time-dependent hydrogen content within a host material, an exact knowledge of the corresponding attenuation coefficient is necessary. Additionally, the effect of scattering has to be considered as it is known to violate Beer's law, which is used to determine the amount of hydrogen from a measured intensity distribution. Within this study, we used a metal hydride inside two different hydrogen storage tanks as host systems, consisting of steel and aluminum. The neutron beam attenuation by hydrogen was investigated in these two different setups during the hydrogen absorption process. A linear correlation to the amount of absorbed hydrogen was found, allowing for a readily quantitative investigation. Further, an analysis of scattering contributions on the measured intensity distributions was performed and is described in detail

  3. Scattering influences in quantitative fission neutron radiography for the in situ analysis of hydrogen distribution in metal hydrides

    Science.gov (United States)

    Börries, S.; Metz, O.; Pranzas, P. K.; Bücherl, T.; Söllradl, S.; Dornheim, M.; Klassen, T.; Schreyer, A.

    2015-10-01

    In situ neutron radiography allows for the time-resolved study of hydrogen distribution in metal hydrides. However, for a precise quantitative investigation of a time-dependent hydrogen content within a host material, an exact knowledge of the corresponding attenuation coefficient is necessary. Additionally, the effect of scattering has to be considered as it is known to violate Beer's law, which is used to determine the amount of hydrogen from a measured intensity distribution. Within this study, we used a metal hydride inside two different hydrogen storage tanks as host systems, consisting of steel and aluminum. The neutron beam attenuation by hydrogen was investigated in these two different setups during the hydrogen absorption process. A linear correlation to the amount of absorbed hydrogen was found, allowing for a readily quantitative investigation. Further, an analysis of scattering contributions on the measured intensity distributions was performed and is described in detail.

  4. Organocatalytic Synthesis of Tetrahydroquinolines from α,β-Unsaturated Ketones via 1,5-Hydride Transfer/Cyclization

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Dae Young [Soonchunhyang Univ., Asan (Korea, Republic of)

    2013-11-15

    We have presented the example of a organo-catalytic enantioselective hydride transfer/cyclization reaction cascade from cyclic amines containing α,β-unsaturated ketones. The synthetically useful ring-fused tetrahydroquinoline derivatives were obtained in moderate to high yields with moderate to high diastereoselectivities. Further investigations for an asymmetric version of this organocatalytic intramolecular redox reaction of α,β-unsaturated ketones are currently underway in our laboratory. The development for direct functionalization of sp{sup 3} C-H bonds has become an area of intense interest in synthetic organic chemistry. Because such reactions offer practical methods for the construction of structurally complex and biologically active organic molecules with atom- and step economy. The 1,5-hydride transfer and subsequent cyclization process is a well-known sp{sup 3} C-H bond function-alization strategy and has attracted considerable interest for its application in the synthesis of heterocyclic compounds.

  5. Refrigeration Performance Analysis and Its Applicability of a New Metal Hydride Couple in Auto Air-conditioning

    Institute of Scientific and Technical Information of China (English)

    NI Jiu-jian; CHEN Jiang-ping; CHEN Zhi-jiu; QIN Feng; L(U) Man-qi; YANG Ke

    2005-01-01

    With COP and dynamic characteristics in refrigeration cycle as criteria,a new metal hydride couple--LaNi4.61Mn0. 26Al0. 13/La0. 6Y0. 4Ni4.8Mn0.2 was selected by establishing calculation procedure and metal hydride selection model. The experimental results show that the refigeration cycle of the selected couple is good in the performance. The recovered waste heat and refrigeration power from exhaust gas of several kinds of automobile are calculated by waste-heat formula,coefficient RQ and COP. Refrigeration cycle of the new couple can satisfy the air-conditioning requirement of truck and car and is not enough in passenger car ,according to the respective cooling load.

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

    Institute of Scientific and Technical Information of China (English)

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

    2004-01-01

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

  7. INFLUENCE OF TEMPERATURE AND PRESSURE ON THE KINETICS OF Mg-6mol%LaNi PREPARED BY HYDRIDING COMBUSTION SYNTHESIS

    Institute of Scientific and Technical Information of China (English)

    Q. Li; K.C. Chou; K.D. Xu; L.J. Jiang; J.Y. Zhang; X.G. Lu

    2006-01-01

    A new model to study the hydriding/dehydriding (H/D) kinetic mechanism has been applied in the two-phase (α-β) region of the Mg-6mol%LaNi composite at temperature and pressure ranging from 523 to 623K and 0.256 to 0.992MPa H2, respectively. The coincidence of the theoretical calculation with the experimental data indicates that the rate-limiting step is hydrogen diffusion in the β phase for hydriding process and the diffusion of hydrogen in the α solid solution for hydrogen desorption with activation energies 89500 and 87900J/mol H2 for H/D processes, respectively, which were much smaller than those of MgH2 and can be attributed to the La and Ni additions.

  8. Alkane Activation Initiated by Hydride Transfer: Co-conversion of Propane and Methanol over H-ZSM-5 Zeolite.

    Science.gov (United States)

    Yu, Si-Min; Wu, Jian-Feng; Liu, Chong; Liu, Wei; Bai, Shi; Huang, Jun; Wang, Wei

    2015-06-15

    Co-conversion of alkane with another reactant over zeolite catalysts has emerged as a new approach to the long-standing challenge of alkane transformation. With the aid of solid-state NMR spectroscopy and GC-MS analysis, it was found that the co-conversion of propane and methanol can be readily initiated by hydride transfer at temperatures of ≥449 K over the acidic zeolite H-ZSM-5. The formation of (13)C-labeled methane and singly (13)C-labeled n-butanes in selective labeling experiments provided the first evidence for the initial hydride transfer from propane to surface methoxy intermediates. The results not only provide new insight into carbocation chemistry of solid acids, but also shed light on the low-temperature transformation of alkanes for industrial applications. PMID:25959356

  9. Studies of hydrogen absorption and desorption processes in advanced intermetallic hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Sato, Masashi

    2005-07-01

    This work is a part of the research program performed in the Department of Energy Systems, Institute for Energy Technology (Kjeller, Norway), which is focused on the development of the advanced hydrogen storage materials. The activities are aimed on studies of the mechanisms of hydrogen interactions with intermetallic alloys with focus on establishing an interrelation between the crystal structure, thermodynamics and kinetics of the processes in the metal-hydrogen systems, on the one hand, and hydrogen storage properties (capacity, rates of desorption, hysteresis). Many of the materials under investigation have potential to be applied in applications, whereas some already have been commercialised in the world market. A number of metals take up considerable amounts of hydrogen and form chemical compounds with H, metal hydrides. Unfortunately, binary hydrides are either very stable (e.g. for the rare earth metals [RE], Zr, Ti, Mg: metal R) or are formed at very high applied pressures of hydrogen gas (e.g. for the transition metals, Ni, Co, Fe, etc.: Metal T). However, hydrogenation process becomes easily reversible at very convenient from practical point of view conditions, around room temperature and at H2 pressures below 1 MPa for the two-component intermetallic alloys R{sub x}T{sub y}. This raised and maintains further interest to the intermetallic hydrides as solid H storage materials. Materials science research of this thesis is focused on studies of the reasons staying behind the beneficial effect of two non-transition elements M(i.e., In and Sn) contributing to the formation of the ternary intermetallic alloys R{sub x}T{sub y}M{sub 2}., on the hydrogen storage behaviours. Particular focus is on two aspects where the remarkable improvement of ordinary metal hydrides is achieved via introduction of In and Sn: a) Increase of the volume density of stored hydrogen in solid materials to the record high level. b) Improvement of the kinetics of hydrogen charge and

  10. Steric effect for proton, hydrogen-atom, and hydride transfer reactions with geometric isomers of NADH-model ruthenium complexes.

    Science.gov (United States)

    Cohen, Brian W; Polyansky, Dmitry E; Achord, Patrick; Cabelli, Diane; Muckerman, James T; Tanaka, Koji; Thummel, Randolph P; Zong, Ruifa; Fujita, Etsuko

    2012-01-01

    Two isomers, [Ru(1)]2+ (Ru = Ru(bpy)2, bpy = 2,2'-bipyridine, 1 = 2-(pyrid-2'-yl)-1-azaacridine) and [Ru(2)]2+ (2 = 3-(pyrid-2'-yl)-4-azaacridine), are bioinspired model compounds containing the nicotinamide functionality and can serve as precursors for the photogeneration of C-H hydrides for studying reactions pertinent to the photochemical reduction of metal-C1 complexes and/or carbon dioxide. While it has been shown that the structural differences between the azaacridine ligands of [Ru(1)]2+ and [Ru(2)]2+ have a significant effect on the mechanism of formation of the hydride donors, [Ru(1HH)]2+ and [Ru(2HH)]2+, in aqueous solution, we describe the steric implications for proton, net-hydrogen-atom and net-hydride transfer reactions in this work. Protonation of [Ru(2*-)] in aprotic and even protic media is slow compared to that of [Ru(1*-)]+. The net hydrogen-atom transfer between *[Ru(1)]2+ and hydroquinone (H2Q) proceeds by one-step EPT, rather than stepwise electron-proton transfer. Such a reaction was not observed for *[Ru(2)]2+ because the non-coordinated N atom is not easily available for an interaction with H2Q. Finally, the rate of the net hydride ion transfer from [Ru(1HH)]2+ to [Ph3C]+ is significantly slower than that of [Ru (2HH)]2+ owing to steric congestion at the donor site. PMID:22470971

  11. A thermally stable gold(III) hydride: synthesis, reactivity, and reductive condensation as a route to gold(II) complexes.

    Science.gov (United States)

    Roşca, Dragoş-Adrian; Smith, Dan A; Hughes, David L; Bochmann, Manfred

    2012-10-15

    Going for gold: The first thermally stable gold(III) hydride [(C N C)*AuH] is presented. It undergoes regioselective insertions with allenes to give gold(III) vinyl complexes, and reductive condensation with [(C N C)*AuOH] to the air-stable Au(II) product, [(C N C)*(2)Au(2)], with a short nonbridged gold-gold bond.

  12. Polarization of modified titanium and titanium–zirconium creates nano-structures while hydride formation is modulated

    Energy Technology Data Exchange (ETDEWEB)

    Frank, Matthias J.; Walter, Martin S. [Department of Biomaterials, Institute for Clinical Dentistry, University of Oslo, PO Box 1109 Blindern, NO-0317 Oslo (Norway); Institute of Medical and Polymer Engineering, Chair of Medical Engineering, Technische Universität München, Boltzmannstrasse 15, D-85748 Garching (Germany); Bucko, Miroslaw M. [Department of Ceramics and Refractory Materials, Faculty of Materials Science and Ceramics, AGH University of Science and Technology, Al Mickiewicza 30, 30-059 Krakow (Poland); Pamula, Elzbieta [Department of Biomaterials, Faculty of Materials Science and Ceramics, AGH University of Science and Technology, Al Mickiewicza 30, 30-059 Krakow (Poland); Lyngstadaas, S. Petter [Department of Biomaterials, Institute for Clinical Dentistry, University of Oslo, PO Box 1109 Blindern, NO-0317 Oslo (Norway); Haugen, Håvard J., E-mail: h.j.haugen@odont.uio.no [Department of Biomaterials, Institute for Clinical Dentistry, University of Oslo, PO Box 1109 Blindern, NO-0317 Oslo (Norway)

    2013-10-01

    The majority of titanium based bone-level dental implants available on the market today feature a sand-blasted and acid-etched (SBAE) surface that contains comparably high hydrogen levels. Cathodic polarization of titanium in acidic solutions is known to further increase titanium hydride on the surface. The aim of this study was to explore the effect of cathodic reduction on titanium (Ti) and titanium–zirconium (TiZr) with a SBAE surface in order to investigate the potential of such a process for further improving surfaces for bone anchored dental implants. Samples of both materials were cathodically polarized in acidic solution at different current densities and for different process times. Chemical analysis of the hydrogen levels by SIMS showed that cathodic reduction re-arranged the hydride already present on the surfaces from the etching process but could not significantly increase hydride levels. The hydrogen layer created by the preceding hot acid etching appeared to modulate further hydride creation. Analysis of the surface topography by SEM showed changes to the nano-topography of both materials after polarization. TiZr showed homogeneously distributed nano-spheres as they were already observed for TiZr SBAE at increased size of 80–100 nm on the whole surface. By contrast, polarization of Ti created nano-nodules and nano-spheres of 150–200 nm on the surface. These spheres were interconnected to form flower-like structures along the ridges and peaks of the surface. Moreover the flanks were covered by a rippled structure of isotropically distributed small-diameter (10–20 nm) nano-nodules.

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

    OpenAIRE

    Cheng, Liang; Doubleday, Charles; Breslow, Ronald

    2015-01-01

    This paper describes experimental and computational evidence that the hydride shift that converts glyceraldehyde to dihydroxyacetone at basic pH with Ca2+ catalysis proceeds primarily by quantum tunneling. This answers the last question about the mechanism of the formose reaction, in which formaldehyde is converted to higher sugars under these conditions. This reaction has long been seen as an important clue to the formation of molecules needed for life under prebiotic conditions on Earth. Ea...

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

    Indian Academy of Sciences (India)

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

    2013-04-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-07-15

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

  16. Process variables in the obtention of U-Mo powder by the hydriding-milling-dehydriding method (HMD process)

    International Nuclear Information System (INIS)

    In the next few years nuclear fuels based on uranium oxides, aluminides and silicides for MTR reactors will be replaced by the high density alloy uranium- 7% (w/w) molybdenum (U-7 Mo). Actually there is only one commercial supplier of this raw material that has to be provided as powder containing 20% enriched uranium (235U). In the Nuclear Fuels Department of the National Atomic Energy Commission (CNEA) at Buenos Aires was developed an alternative way of producing U-7 Mo powder in a production scale. Meanwhile CNEA is participating in the International Program (RERTR) for final qualification of this nuclear material. This new method of production consists in the hydriding of the alloy, milling the hydride to final size and dehydriding the powder. These results were achieved because a special technique was discovered for the massive hydriding of the U-7 Mo alloy. The production method is simple, requires conventional equipment and low investment. Argentine can have important comparative advantages for its production and exportation. A scale production plant is being planed. (author)

  17. Flame-in-gas-shield and miniature diffusion flame hydride atomizers for atomic fluorescence spectrometry: optimization and comparison

    International Nuclear Information System (INIS)

    A detailed optimization of relevant experimental parameters of two hydride atomizers for atomic fluorescence spectrometry: flame-in-gas-shield atomizer with a two-channel shielding unit and a standard atomizer for atomic fluorescence spectrometry, miniature diffusion flame, was performed. Arsine, generated by the reaction with NaBH4 in a flow injection arrangement, was chosen as the model hydride. Analytical characteristics of both the atomizers (sensitivity, noise, limits of detection) were compared. Under optimum conditions sensitivity obtained with flame-in-gas-shield atomizer was approximately twice higher than with miniature diffusion flame. The additional advantage of flame-in-gas-shield atomizer is significantly lower flame emission resulting in a better signal to noise ratio. The resulting arsenic limits of detection for miniature diffusion flame and flame-in-gas-shield atomizer were 3.8 ng l−1 and 1.0 ng l−1, respectively. - Highlights: • We optimized and compared two hydride atomizers for atomic fluorescence spectrometry. • Miniature diffusion flame and flame-in-gas-shield atomizer were optimized. • The limit of detection for arsenic was 1.0 ng l−1

  18. Facile synthesis of Ba1-xKxFe₂As₂ superconductors via hydride route

    Energy Technology Data Exchange (ETDEWEB)

    Zaikina, Julia V. [Univ. of California at Davis, Davis, CA (United States); Batuk, Maria [Univ. of Antwerp, Antwerp (Belgium); Abakumov, Artem M. [Univ. of Antwerp, Antwerp (Belgium); Navrotsky, Alexandra [Univ. of California at Davis, Davis, CA (United States); Kauzlarich, Susan M. [Univ. of California at Davis, Davis, CA (United States)

    2014-12-03

    We have developed a fast, easy, and scalable synthesis method for Ba1-xKxFe₂As₂ (0 ≤ x ≤ 1) superconductors using hydrides BaH₂ and KH as a source of barium and potassium metals. Synthesis from hydrides provides better mixing and easier handling of the starting materials, consequently leading to faster reactions and/or lower synthesis temperatures. The reducing atmosphere provided by the evolved hydrogen facilitates preparation of oxygen-free powders. By a combination of methods we have shown that Ba1-xKxFe₂As₂ obtained via hydride route has the same characteristics as when it is prepared by traditional solid-state synthesis. Refinement from synchrotron powder X-ray diffraction data confirms a linear dependence of unit cell parameters upon K content as well as the tetragonal to orthorhombic transition at low temperatures for compositions with x < 0.2. Magnetic measurements revealed dome-like dependence of superconducting transition temperature Tc upon K content with a maximum of 38 K for x close to 0.4. Electron diffraction and high-resolution high-angle annular dark-field scanning transmission electron microscopy indicates an absence of Ba/K ordering, while local inhomogeneity in the Ba/K distribution takes place at a scale of several angstroms along [110] crystallographic direction.

  19. Flame-in-gas-shield and miniature diffusion flame hydride atomizers for atomic fluorescence spectrometry: optimization and comparison

    Energy Technology Data Exchange (ETDEWEB)

    Marschner, Karel, E-mail: karel.marschner@biomed.cas.cz [Institute of Analytical Chemistry of the ASCR, v. v. i., Veveří 97, 602 00 Brno (Czech Republic); Charles University in Prague, Faculty of Science, Department of Analytical Chemistry, Albertov 8, 128 43 Prague (Czech Republic); Musil, Stanislav; Dědina, Jiří [Institute of Analytical Chemistry of the ASCR, v. v. i., Veveří 97, 602 00 Brno (Czech Republic)

    2015-07-01

    A detailed optimization of relevant experimental parameters of two hydride atomizers for atomic fluorescence spectrometry: flame-in-gas-shield atomizer with a two-channel shielding unit and a standard atomizer for atomic fluorescence spectrometry, miniature diffusion flame, was performed. Arsine, generated by the reaction with NaBH{sub 4} in a flow injection arrangement, was chosen as the model hydride. Analytical characteristics of both the atomizers (sensitivity, noise, limits of detection) were compared. Under optimum conditions sensitivity obtained with flame-in-gas-shield atomizer was approximately twice higher than with miniature diffusion flame. The additional advantage of flame-in-gas-shield atomizer is significantly lower flame emission resulting in a better signal to noise ratio. The resulting arsenic limits of detection for miniature diffusion flame and flame-in-gas-shield atomizer were 3.8 ng l{sup −1} and 1.0 ng l{sup −1}, respectively. - Highlights: • We optimized and compared two hydride atomizers for atomic fluorescence spectrometry. • Miniature diffusion flame and flame-in-gas-shield atomizer were optimized. • The limit of detection for arsenic was 1.0 ng l{sup −1}.

  20. Mechanism of the sulfurisation of phosphines and phosphites using 3-amino-1,2,4-dithiazole-5-thione (xanthane hydride).

    Science.gov (United States)

    Hanusek, Jirí; Russell, Mark A; Laws, Andrew P; Jansa, Petr; Atherton, John H; Fettes, Kevin; Page, Michael I

    2007-02-01

    Contrary to a previous report, the sulfurisation of phosphorus(III) derivatives by 3-amino-1,2,4-dithiazole-5-thione (xanthane hydride) does not yield carbon disulfide and cyanamide as the additional reaction products. The reaction of xanthane hydride with triphenyl phosphine or trimethyl phosphite yields triphenyl phosphine sulfide or trimethyl thiophosphate, respectively, and thiocarbamoyl isothiocyanate which has been trapped with nucleophiles. The reaction pathway involves initial nucleophilic attack of the phosphorus at sulfur next to the thiocarbonyl group of xanthane hydride followed by decomposition of the phosphonium intermediate formed to products. The Hammett rho-values for the sulfurisation of substituted triphenyl phosphines and triphenyl phosphites in acetonitrile are approximately -1.0. The entropies of activation are very negative (-114+/-15 J mol-1 K-1) with little dependence on solvent which is consistent with a bimolecular association step leading to the transition state. The negative values of DeltaS(not equal) and rho values indicate that the rate limiting step of the sulfurisation reaction is formation of the phosphonium ion intermediate which has an early transition state with little covalent bond formation. The site of nucleophilic attack has been also confirmed using computational calculations. PMID:17252130

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

    Science.gov (United States)

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

    2008-08-14

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

  2. FY 2016 Status Report: CIRFT Testing on Spent Nuclear Fuels and Hydride Reorientation Study

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jy-An John [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division; Wang, Hong [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division; Yan, Yong [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division; Bevard, Bruce B. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division; Scaglione, John M. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division

    2016-08-04

    This report provides a detailed description of the Cyclic Integrated Reversible-Bending Fatigue Tester (CIRFT) testing conducted on spent nuclear fuel (SNF) rods in FY 2016, including hydride reorientation test results. Contact-based measurement, or three-LVDT-based curvature measurement, of SNF rods has proven to be quite reliable in CIRFT testing. However, how the linear variable differential transformer (LVDT) head contacts the SNF rod may have a significant effect on the curvature measurement, depending on the magnitude and direction of rod curvature. To correct such contact/curvature issues, sensor spacing, defined as the amount of separation between the three LVDT probes, is a critical measurement that can be used to calculate rod curvature once the deflections are obtained. Recently developed CIRFT data analyses procedures were integrated into FY 2016 CIRFT testing results for the curvature measurements. The variations in fatigue life are provided in terms of moment, equivalent stress, curvature, and equivalent strain for the tested SNFs. The equivalent stress plot collapsed the data points from all of the SNFs into a single zone. A detailed examination revealed that, at same stress level, fatigue lives display a descending order as follows: H. B. Robinson Nuclear Power Station (HBR), Limerick Nuclear Power Station (LMK), mixed uranium-plutonium oxide (MOX). If looking at the strain, then LMK fuel has a slightly longer fatigue life than HBR fuel, but the difference is subtle. The knee point of endurance limit in the curve of moment and curvature or equivalent quantities is more clearly defined for LMK and HBR fuels. The treatment affects the fatigue life of specimens. Both a drop of 12 in. and radial hydride treatment (RHT) have a negative impact on fatigue life. The effect of thermal annealing on MOX fuel rods was relatively small at higher amplitude but became significant at low amplitude of moment. Thermal annealing tended to extend the fatigue life of

  3. Hydrogen storage properties of carbon nanomaterials and carbon containing metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Maehlen, Jan Petter

    2003-07-01

    The topic of this thesis is structural investigations of carbon containing materials in respect to their hydrogen storage properties. This work was initially triggered by reports of extremely high hydrogen storage capacities of specific carbon nanostructures. It was decided to try to verify and understand the mechanisms in play in case of the existence of such high hydrogen densities in carbon. Two different routes towards the goal were employed; by studying selected hydrides with carbon as one of its constituents (mainly employing powder diffraction techniques in combination with hydrogen absorption and desorption measurements) and by carefully conducting hydrogen sorption experiments on what was believed to be the most ''promising'' carbon nanomaterial sample. In the latter case, a lot of effort was attributed to characterisations of different carbon nanomaterial containing samples with the aid of electron microscopy. Three different carbon-containing metal hydride systems, Y2C-H, YCoC-H and Y5SiC0.2-H, were examined. A relation between hydrogen occupation and the local arrangement of metal and carbon atoms surrounding the hydrogen sites was established. Several characteristic features of the compounds were noted in addition to solving the structure of the former unknown deuterideY5Si3C0.2D2.0 by the use of direct methods. Several carbon-nanomaterial containing samples were studied by means of transmission electron microscopy and powder diffraction, thus gaining knowledge concerning the structural aspects of nanomaterials. Based on these investigations, a specific sample containing a large amount of open-ended single-wall carbon nanotubes was chosen for subsequent hydrogen storage experiments. The latter experiments revealed moderate hydrogen storage capacities of the nanotubes not exceeding the values obtained for more conventional forms of carbon. These two different routes in investigating the hydrogen storage properties of carbon and

  4. Continuous flow hydride generation-atomic fluorescence spectrometric determination and speciation of arsenic in wine

    International Nuclear Information System (INIS)

    Methods for the atomic fluorescence spectrometric (AFS) determination of total arsenic and arsenic species in wines based on continuous flow hydride generation (HG) with atomization in miniature diffusion flame (MDF) are described. For hydride-forming arsenic, L-cysteine is used as reagent for pre-reduction and complexation of arsenite, arsenate, monomethylarsonate and dimethylarsinate. Concentrations of hydrochloric acid and tetrahydroborate are optimized in order to minimize interference by ethanol. Procedure permits determination of the sum of these four species in 5-10-fold diluted samples with limit of detection (LOD) 0.3 and 0.6 μg l-1 As in white and red wines, respectively, with precision between 2% and 8% RSD at As levels within 0.5-10 μg l-1. Selective arsine generation from different reaction media is used for non-chromatographic determination of arsenic species in wines: citrate buffer at pH 5.1 for As(III); 0.2 mol l-1 acetic acid for arsenite + dimethylarsinate (DMA); 8 mol l-1 HCl for total inorganic arsenic [As(III) + As(V)]; and monomethylarsonate (MMA) calculated by difference. Calibration with aqueous and ethanol-matched standard solutions of As(III) is used for 10- and 5-fold diluted samples, respectively. The LODs are 0.4 μg l-1 for As(III) and 0.3 μg l-1 for the other three As species and precision is within 4-8% RSDs. Arsenic species in wine were also determined by coupling of ion chromatographic separation on an anion exchange column and HG-flame AFS detection. Methods were validated by means of recovery studies and comparative analyses by HG-AFS and electrothermal atomic absorption spectrometry after microwave digestion. The LODs were 0.12, 0.27, 0.15 and 0.13 μg l-1 (as As) and RSDs were 2-6%, 5-9%, 3-7% and 2-5% for As(III), As(V), MMA and DMA arsenic species, respectively. Bottled red and white wines from Bulgaria, Republic of Macedonia and Italy were analyzed by non-chromatographic and chromatographic procedures and the As

  5. Study on the nature of interaction of pyrrole with various hydrides

    International Nuclear Information System (INIS)

    Graphical abstract: The equilibrium geometries of the pyrrole-HnX (X=F, O, N, Cl, S and P) complexes are shown in above figure. These geometries are classified as N-H...X type and H-π-type (also referred to in this paper as geometry types I and II, respectively). The N-H...X type geometry features a hydrogen bond formed between the hydrogen atom of pyrrole and X atom of HnX, and has C1 symmetry. The π-type geometry is characterized by an H-π bond formed between a hydrogen atom of HnX and the π-electron system of the aromatic ring, and has C1 symmetry. For the pyrrole-HF, H2O, NH3, H2S and -PH3 complexes have N-H...X type and π-type. For the pyrrole-HCl complexes have only H-π-type. Display Omitted Highlights: → We investigated the intermolecular interaction of pyrrole with the various hydrides. → There are N-H...X and H-π-type hydrogen-bonding complexes. → With the exception of pyrrole-H2O and pyrrole-NH3 complexes, all of the other pyrrole-HnX complexes favors π-type H-bonding. → The electrostatic and dispersion interactions dominate the H-π-type complexes. - Abstract: Equilibrium geometries, interaction energies, atomic charge, and charge transfer for the N-H...X and H-π-type hydrogen-bonding complexes between pyrrole and various hydrides HnX (X=F, O, N, Cl, S, and P) were studied at the MP2/aug-cc-pVDZ level. With the exception of pyrrole-H2O and pyrrole-NH3 complexes, all of the other pyrrole-HnX complexes favors π-type H-bonding. To further study the nature of the π-type H-bonding, an SAPT (the symmetry adapted perturbation theory) energy decomposition analysis was carried out and the results indicate that the electrostatic and dispersion interactions dominate the H-π-type complexes.

  6. Electrical, optical, and structural properties of GaN films prepared by hydride vapor phase epitaxy

    Energy Technology Data Exchange (ETDEWEB)

    Polyakov, A.Y. [National University of Science and Technology MISiS, Moscow (Russian Federation); School of Advanced Materials Engineering and Research Center of Advanced Materials Development, Chonbuk National University, Jeonju (Korea, Republic of); Smirnov, N.B. [National University of Science and Technology MISiS, Moscow (Russian Federation); Institute of Rare Metals, Moscow (Russian Federation); Yakimov, E.B. [Institute of Microelectronics Technology and High Purity Materials Russian Academy of Science, Chernogolovka (Russian Federation); Usikov, A.S. [Nitride Crystals, Inc., Deer Park (United States); Saint-Petersburg National Research University of Information Technologies, Mechanics and Optics, Saint Petersburg (Russian Federation); Helava, H. [Nitride Crystals, Inc., Deer Park (United States); Shcherbachev, K.D. [School of Advanced Materials Engineering and Research Center of Advanced Materials Development, Chonbuk National University, Jeonju (Korea, Republic of); Govorkov, A.V. [Institute of Rare Metals, Moscow (Russian Federation); Makarov, Yu N. [Nitride Crystals, Inc., Deer Park (United States); Lee, In-Hwan, E-mail: ihlee@jbnu.ac.kr [School of Advanced Materials Engineering and Research Center of Advanced Materials Development, Chonbuk National University, Jeonju (Korea, Republic of)

    2014-12-25

    Highlights: • GaN films are prepared by hydride vapor phase epitaxy (HVPE). • Residual donors and deep traps show a minimum density versus growth temperature. • This minimum is located close to the HVPE growth temperature of 950 °C. • Good crystalline GaN with residual donor density < 10{sup 16} cm{sup −3} can be grown at 950 °C. - Abstract: Two sets of undoped GaN films with the thickness of 10–20 μm were prepared by hydride vapor phase epitaxy (HVPE) and characterized by capacitance–voltage (C–V) profiling, microcathodoluminescence (MCL) spectra measurements, MCL imaging, electron beam induced current (EBIC) imaging, EBIC dependence on accelerating voltage, deep levels transient spectroscopy, high resolution X-ray diffraction measurements. The difference in growth conditions was mainly related to the lower (850 °C, group 1) or higher (950 °C, group 2) growth temperature. Both groups of samples showed similar crystalline quality with the dislocation density close to 10{sup 8} cm{sup −2}, but very different electrical and optical properties. In group 1 samples the residual donors concentration was ∼10{sup 17} cm{sup −3} or higher, the MCL spectra were dominated by the band-edge luminescence, and the diffusion length of charge carriers was close to 0.1 μm. Group 2 samples had a 2–4.5 μm thick highly resistive layer on top, for which MCL spectra were determined by green, yellow and red defect bands, and the diffusion length was 1.5 times higher than in group 1. We also present brief results of growth at the “standard” HVPE growth temperature of 1050 °C that show the presence of a minimum in the net donor concentration and deep traps density as a function of the growth temperature. Possible reasons for the observed results are discussed in terms of the electrical compensation of residual donors by deep traps.

  7. 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.

  8. Identification of Si and O donors in hydride-vapor-phase epitaxial GaN

    Science.gov (United States)

    Moore, W. J.; Freitas, J. A.; Braga, G. C. B.; Molnar, R. J.; Lee, S. K.; Lee, K. Y.; Song, I. J.

    2001-10-01

    Donor impurity excitation spectra in the infrared from two high-quality, not-intentionally doped, hydride-vapor-phase epitaxial GaN wafers are reported. Two previously observed shallow donors which we designate N1 and N2 were observed in both wafers. However, spectra of one wafer are dominated by N1 and spectra of the other by N2. A comparison of infrared and secondary ion mass spectroscopic data allows identification of N1 as Si and N2 as O. Silicon is the shallowest uncompensated donor in these samples with an activation energy of 30.18±0.1 meV in the freestanding Samsung wafer. The activation energy of O is found to be 33.20±0.1 meV. An unidentified third donor with an activation energy of 31.23±0.1 meV also was observed. Integrated absorption cross sections are found to be 8.5×10-14 cm for Si and 8.6×10-14 cm for O.

  9. Determination of inorganic species of Sb and Te in cereals by hydride generation atomic fluorescence spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Reyes, Mariela N.M.; Cervera, Maria L.; Guardia, Miguel de la, E-mail: m.luisa.cervera@uv.e [University of Valencia, Valencia (Spain). Dept. of Analytical Chemistry

    2011-07-01

    A non-chromatographic fast, sensitive and easy method has been developed for the determination of Sb(III), Sb(V), Te(IV) and Te(VI) in cereal samples. The procedure is based on ultrasound assisted extraction and determination by hydride generation atomic fluorescence spectrometry (HG AFS). Preliminary studies were made in order to get the best extraction efficiency using 1 mol L{sup -1} phosphoric acid, 1 mol L{sup -1} nitric acid, aqua regia, 1 mol L{sup -1} sulfuric acid and 6 mol L{sup -1} hydrochloric acid. The extraction with aqua regia showed a clear interconversion of the species during the process, being H{sub 2}SO{sub 4} the best extractant with efficiencies greater than 90% from the total content of Sb and Te quantified previously and without species interconversion. This point was checked by recovery experiments at different spiked levels. The method provided limits of detection values from 0.1 to 0.5 ng g{sup -1} with relative standard deviation values from 5.4 to 9.2% of 10 independent analysis of samples containing few ng g-1 of Sb and Te species. (author)

  10. Determination of inorganic species of Sb and Te in cereals by hydride generation atomic fluorescence spectrometry

    International Nuclear Information System (INIS)

    A non-chromatographic fast, sensitive and easy method has been developed for the determination of Sb(III), Sb(V), Te(IV) and Te(VI) in cereal samples. The procedure is based on ultrasound assisted extraction and determination by hydride generation atomic fluorescence spectrometry (HG AFS). Preliminary studies were made in order to get the best extraction efficiency using 1 mol L-1 phosphoric acid, 1 mol L-1 nitric acid, aqua regia, 1 mol L-1 sulfuric acid and 6 mol L-1 hydrochloric acid. The extraction with aqua regia showed a clear interconversion of the species during the process, being H2SO4 the best extractant with efficiencies greater than 90% from the total content of Sb and Te quantified previously and without species interconversion. This point was checked by recovery experiments at different spiked levels. The method provided limits of detection values from 0.1 to 0.5 ng g-1 with relative standard deviation values from 5.4 to 9.2% of 10 independent analysis of samples containing few ng g-1 of Sb and Te species. (author)

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

    Energy Technology Data Exchange (ETDEWEB)

    Weiss, Paul

    2014-01-20

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

  12. Pyrometallurgical Extraction of Valuable Elements in Ni-Metal Hydride Battery Electrode Materials

    Science.gov (United States)

    Jiang, Yin-ju; Deng, Yong-chun; Bu, Wen-gang

    2015-10-01

    Gas selective reduction-oxidation (redox) and melting separation were consecutively applied to electrode materials of AB5-type Ni-metal hydride batteries leading to the production of a Ni-Co alloy and slag enriched with rare earth oxides (REO). In the selective redox process, electrode materials were treated with H2/H2O at 1073 K and 1173 K (800 °C and 900 °C). Active elements such as REs, Al, and Mn were oxidized whereas relatively inert elements such as Ni and Co were transformed into their elemental states in the treated materials. SiO2 and Al2O3 powders were added into the treated materials as fluxes which were then melted at 1823 K (1550 °C) to yield a Ni-Co alloy and a REO-SiO2-Al2O3-MnO slag. The high-purity Ni-Co alloy produced can be used as a raw material for AB5-type hydrogen-storage alloy. The REO content in slag was very high, i.e., 48.51 pct, therefore it can be used to recycle rare earth oxides.

  13. Effect of surface modification of metal hydride electrode on performance of MH/Ni batteries

    Institute of Scientific and Technical Information of China (English)

    YANG Kai; WU Feng; CHEN Shi; ZHANG Cun-zhong

    2007-01-01

    A novel method was applied to the surface modification of the metal hydride(MH) electrode of MH/Ni batteries. Both sides of the electrode were plated with a thin silver film about 0.1μm thick using vacuum evaporation plating technology, and the effect of the electrode on the performance of MH/Ni batteries was examined. It is found that the surface modification can enhance the electrode conductivity and decrease the battery ohimic resistance. After surface modification, the discharge capacity at 5C (7.5A) is increased by 212 mA·h and the discharge voltage is increased by 0.11 V, the resistance of the batteries is also decreased by 32%. The batteries with modified electrode exhibit satisfactory durability. The remaining capacity of the modified batteries is 89% of the initial capacity even after 500 cycles. The inner pressure of the batteries during overcharging is lowered and the charging efficiency of the batteries is improved.

  14. The Importance of Rare-Earth Additions in Zr-Based AB2 Metal Hydride Alloys

    Directory of Open Access Journals (Sweden)

    Kwo-Hsiung Young

    2016-07-01

    Full Text Available Effects of substitutions of rare earth (RE elements (Y, La, Ce, and Nd to the Zr-based AB2 multi-phase metal hydride (MH alloys on the structure, gaseous phase hydrogen storage (H-storage, and electrochemical properties were studied and compared. Solubilities of the RE atoms in the main Laves phases (C14 and C15 are very low, and therefore the main contributions of the RE additives are through the formation of the RENi phase and change in TiNi phase abundance. Both the RENi and TiNi phases are found to facilitate the bulk diffusion of hydrogen but impede the surface reaction. The former is very effective in improving the activation behaviors. −40 °C performances of the Ce-doped alloys are slightly better than the Nd-doped alloys but not as good as those of the La-doped alloys, which gained the improvement through a different mechanism. While the improvement in ultra-low-temperature performance of the Ce-containing alloys can be associated with a larger amount of metallic Ni-clusters embedded in the surface oxide, the improvement in the La-containing alloys originates from the clean alloy/oxide interface as shown in an earlier transmission electron microscopy study. Overall, the substitution of 1 at% Ce to partially replace Zr gives the best electrochemical performances (capacity, rate, and activation and is recommended for all the AB2 MH alloys for electrochemical applications.

  15. 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

  16. Broken-Symmetry Unrestricted Hybrid Density Functional Calculations on Nickel Dimer and Nickel Hydride

    CERN Document Server

    Diaconu, C V; Doll, J D; Freeman, D L; Diaconu, Cristian V.; Cho, Art E.; Freeman, David L.

    2004-01-01

    In the present work we investigate the adequacy of broken-symmetry (BS) unrestricted (U) density functional theory (DFT) for constructing the potential energy curve of nickel dimer and nickel hydride, as model for larger bare and hydrogenated nickel cluster calculations. We use three hybrid functionals: B3LYP, Becke98, and FSLYP (50% Hartree-Fock and 50% Slater exchange and LYP correlation functional) with two basis sets: all-electron (AE) Wachters+f basis set and Stuttgart RSC effective core potential (ECP) and basis set. We find that, overall, B3LYP functional with Wachters+f AE basis set performs best, with only 1.3% root-mean-square (RMS) deviation from experiment, followed by Becke98/AE and B3LYP/ECP, with RMS deviation from experimental value of 2.5% and 2.7%, respectively. We also find that for Ni dimer, the spin-projection for the broken-symmetry unrestricted singlet states changes the ordering of the states, but the splittings are less than 10 meV. All our calculations predict a (delta)(delta)-hole g...

  17. Herschel-HIFI detections of hydrides towards AFGL 2591 (Envelope emission versus tenuous cloud absorption)

    CERN Document Server

    Bruderer, S; van Dishoeck, E F; Melchior, M; Doty, S D; van der Tak, F; Stäuber, P; Wampfler, S F; Dedes, C; Yıldız, U A; Pagani, L; Giannini, T; de Graauw, Th; Whyborn, N; Teyssier, D; Jellema, W; Shipman, R; Schieder, R; Honingh, N; Caux, E; Bächtold, W; Csillaghy, A; Monstein, C; Bachiller, R; Baudry, A; Benedettini, M; Bergin, E; Bjerkeli, P; Blake, G A; Bontemps, S; Braine, J; Caselli, P; Cernicharo, J; Codella, C; Daniel, F; di Giorgio, A M; Dominik, C; Encrenaz, P; Fich, M; Fuente, A; Goicoechea, J R; Helmich, F; Herczeg, G J; Herpin, F; Hogerheijde, M R; Jacq, T; Johnstone, D; Jørgensen, J K; Kristensen, L E; Larsson, B; Lis, D; Liseau, R; Marseille, M; McCoey, C; Melnick, G; Neufeld, D; Nisini, B; Olberg, M; Parise, B; Pearson, J C; Plume, R; Risacher, C; Santiago-Garcia, J; Saraceno, P; Shipman, R; Tafalla, M; van Kempen, T A; Visser, R; Wyrowski, F

    2010-01-01

    The Heterodyne Instrument for the Far Infrared (HIFI) onboard the Herschel Space Observatory allows the first observations of light diatomic molecules at high spectral resolution and in multiple transitions. Here, we report deep integrations using HIFI in different lines of hydrides towards the high-mass star forming region AFGL 2591. Detected are CH, CH+, NH, OH+, H2O+, while NH+ and SH+ have not been detected. All molecules except for CH and CH+ are seen in absorption with low excitation temperatures and at velocities different from the systemic velocity of the protostellar envelope. Surprisingly, the CH(JF,P = 3/2_2,- - 1/2_1,+) and CH+(J = 1 - 0, J = 2 - 1) lines are detected in emission at the systemic velocity. We can assign the absorption features to a foreground cloud and an outflow lobe, while the CH and CH+ emission stems from the envelope. The observed abundance and excitation of CH and CH+ can be explained in the scenario of FUV irradiated outflow walls, where a cavity etched out by the outflow al...

  18. Effect of Nano-Magnesium Hydride on the Thermal Decomposition Behaviors of RDX

    Directory of Open Access Journals (Sweden)

    Miao Yao

    2013-01-01

    Full Text Available In order to improve the detonation performance of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX explosive, addictives with high heat values were used, and magnesium hydride (MgH2 is one of the candidates. However, it is important to see whether MgH2 is a safe addictive. In this paper, the thermal and kinetic properties of RDX and mixture of RDX/MgH2 were investigated by differential scanning calorimeter (DSC and accelerating rate calorimeter (ARC, respectively. The apparent activation energy (E and frequency factor (A of thermal explosion were calculated based on the data of DSC experiments using the Kissinger and Ozawa approaches. The results show that the addition of MgH2 decreases both E and A of RDX, which means that the mixture of RDX/MgH2 has a lower thermal stability than RDX, and the calculation results obtained from the ARC experiments data support this too. Besides, the most probable mechanism functions about the decomposition of RDX and RDX/MgH2 were given in this paper which confirmed the change of the decomposition mechanism.

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

    International Nuclear Information System (INIS)

    Three-dimensional (3D) photonic crystals are one class of materials where epitaxy, and the resultant attractive electronic properties, would enable new functionalities for optoelectronic devices. Here we utilize self-assembled colloidal templates to fabricate epitaxially grown single crystal 3D mesostructured GaxIn1−xP (GaInP) semiconductor photonic crystals using hydride vapor phase epitaxy (HVPE). The epitaxial relationship between the 3D GaInP and the substrate is preserved during the growth through the complex geometry of the template as confirmed by X-ray diffraction (XRD) and high resolution transmission electron microscopy. XRD reciprocal space mapping of the 3D epitaxial layer further demonstrates the film to be nearly fully relaxed with a negligible strain gradient. Fourier transform infrared spectroscopy reflection measurement indicates the optical properties of the photonic crystal which agree with finite difference time domain simulations. This work extends the scope of the very few known methods for the fabrication of epitaxial III-V 3D mesostructured materials to the well-developed HVPE technique

  20. Gradual variation method for thick GaN heteroepitaxy by hydride vapour phase epitaxy

    Institute of Scientific and Technical Information of China (English)

    Du Yan-Hao; Wu Jie-Jun; Luo Wei-Ke; John Goldsmith; Han Tong; Tao Yue-Bin; Yang Zhi-Jian; Yu Tong-Jun; Zhang Guo-Yi

    2011-01-01

    Two strain-state samples of GaN,labelled the strain-relief sample and the quality-improved sample,were grown by hydride vapour phase epitaxy (HVPE),and then characterized by high-resolution X-ray diffraction,photoluminescence and optical microscopy. Two strain states of GaN in HVPE,like 3D and 2D growth modes in metal-organic chemical vapour deposition (MOCVD),provide an effective way to solve the heteroepitaxial problems of both strain relief and quality improvement. The gradual variation method (GVM),developed based on the two strain states,is characterized by growth parameters' gradual variation alternating between the strain-relief growth conditions and the qualityimproved growth conditions. In GVM,the introduction of the strain-relief amplitude,which is defined by the range from the quality-improved growth conditions to the strain-relief growth conditions,makes the strain-relief control concise and effective. The 300-4m thick bright and crack-free GaN film grown on a two-inch sapphire proves the effectiveness of GVM.

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

    KAUST Repository

    Soignier, Sophie

    2014-01-01

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

  2. Solar photovoltaic charging of high voltage nickel metal hydride batteries using DC power conversion

    Science.gov (United States)

    Kelly, Nelson A.; Gibson, Thomas L.

    There are an increasing number of vehicle choices available that utilize batteries and electric motors to reduce tailpipe emissions and increase fuel economy. The eventual production of electricity and hydrogen in a renewable fashion, such as using solar energy, can achieve the long-term vision of having no tailpipe environmental impact, as well as eliminating the dependence of the transportation sector on dwindling supplies of petroleum for its energy. In this report we will demonstrate the solar-powered charging of the high-voltage nickel-metal hydride (NiMH) battery used in the GM 2-mode hybrid system. In previous studies we have used low-voltage solar modules to produce hydrogen via the electrolysis of water and to directly charge lithium-ion battery modules. Our strategy in the present work was to boost low-voltage PV voltage to over 300 V using DC-DC converters in order to charge the high-voltage NiMH battery, and to regulate the battery charging using software to program the electronic control unit supplied with the battery pack. A protocol for high-voltage battery charging was developed, and the solar to battery charging efficiency was measured under a variety of conditions. We believe this is the first time such high-voltage batteries have been charged using solar energy in order to prove the concept of efficient, solar-powered charging for battery-electric vehicles.

  3. Evaluation of U-Zr hydride fuel for a thorium fuel cycle in an RTR concept

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Kyung Taek; Cho, Nam Zin [Korea Advanced Institute of Science and Technology, Taejon (Korea, Republic of)

    1998-12-31

    In this paper, we performed a design study of a thorium fueled reactor according to the design concept of the Radkowsky Thorium Reactor (RTR) and evaluated its overall performance. To enhance its performance and alleviate its problems, we introduced a new metallic uranium fuel, uranium-zirconium hydride (U-ZrH{sub 1.6}), as a seed fuel. For comparison, typical ABB/CE-type PWR based on SYSTEM 80+and standard RTR-type thorium reactor were also studied. From the results of performance analysis, we could ascertain advantages of RTR-type thorium fueled reactor in proliferation resistance, fuel cycle economics, and back-end fuel cycle. Also, we found that enhancement of proliferation resistance and safer operating conditions may be achieved by using the U-ZrH{sub 1.6} fuel in the seed region without additional penalties in comparison with the standard RTR`s U-Zr fuel. 6 refs., 2 figs., 6 tabs. (Author)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-12-14

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

  5. Crystal structure determination and reaction pathway of amide-hydride mixtures

    International Nuclear Information System (INIS)

    Combined synchrotron in situ X-ray diffraction and neutron diffraction studies were performed on 2:1 mixtures of lithium amide and magnesium hydride, which have shown promise as solid-state hydrogen storage materials. The dehydrogenated product is a mixed lithium and magnesium imide, Li2Mg(NH)2, whose crystal structure has not heretofore been determined. Furthermore, at elevated temperatures, Li2Mg(NH)2 undergoes two structural transitions from an orthorhombic structure to a primitive cubic structure at intermediate temperature (350 deg. C) followed by a face-centered cubic crystal structure at high temperature (500 deg. C). Disordering of the Li, Mg and cation vacancies as a function of temperature drives the structural transitions. We report the reaction pathway from in situ X-ray diffraction studies and the crystal structures of the three structural variants of Li2Mg(NH)2 as determined by high-resolution X-ray and neutron powder diffraction. We also report the hydrogen storage reaction pathways for mixtures with other cation ratios

  6. Nucleation of GaN on sapphire substrates at intermediate temperatures by Hydride Vapor Phase Epitaxy

    Energy Technology Data Exchange (ETDEWEB)

    Lukin, G.; Niederschlag, E.; Paetzold, O.; Stelter, M. [Institute of Nonferrous Metallurgy and Purest Materials, TU Bergakademie Freiberg (Germany); Roeder, C.; Kortus, J. [Institute of Theoretical Physics, TU Bergakademie Freiberg (Germany); Shashev, Y.; Muehle, U.; Rafaja, D. [Institute of Materials Science, TU Bergakademie Freiberg (Germany)

    2012-02-15

    A novel approach to deposit GaN layers directly on a sapphire substrate by Hydride Vapor Phase Epitaxy is presented. The two-step deposition process includes the growth of GaN nucleation layers at intermediate temperatures in the range of 750 - 900 C and subsequent high-temperature overgrowth at about 1040 C. Closed and non-closed nucleation layers with a thickness of up to 2 {mu}m were produced and characterized by scanning and transmission electron microscopy, micro-Raman spectroscopy and X-ray diffraction. A growth temperature of 780 C is found to be optimal with respect to density and size distribution of nucleation islands. Raman measurements performed on the nucleation layers reveal nearly zero residual stress indicating effective stress relaxation on cooling down from growth temperature. The results of first overgrowth experiments demonstrate the possibility to grow 10 {mu}m thick, crack-free GaN layers of high crystalline quality on the nucleation layers. (copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  7. Computational fluid dynamics-aided analysis of a hydride vapor phase epitaxy reactor

    Science.gov (United States)

    Schulte, Kevin L.; Simon, John; Roy, Abhra; Reedy, Robert C.; Young, David L.; Kuech, Thomas F.; Ptak, Aaron J.

    2016-01-01

    We report the development of a computational fluid dynamics (CFD) model of a dual chamber hydride vapor phase epitaxial (HVPE) growth reactor. Uniformity of reactant concentrations in the growth stream, transient reactor flows, and cross doping between the two growth chambers, all factors critical to the deposition of uniform, low defect semiconductor layers, were modeled. Simulation results were generated by solving the fundamental continuity, momentum and energy equations over a discretized reactor volume by a finite volume analysis with the aid of CFD-ACE+ commercial software. We demonstrated uniformity of the vapor composition within ±1% across the substrate, achieved due to specific features of the reactor design. Small compositional non-uniformity (±2% absolute) in In1-xGaxP layers grown in our reactor was correlated with calculated temperature non-uniformity across the substrate. Gas switching was modeled and the transient time predicted by the model was confirmed by measurement of doping transients in a sample grown in the reactor. Lastly the gas curtains that chemically isolate the reactor chambers were modeled and the results were compared to experimental data for cross doping between the chambers. As an example, we demonstrate, based on insight from the model, that our HVPE reactor is suitable for the deposition of GaAs PV devices. CFD modeling is a critical tool for the scale up of laboratory level processes to industrial levels.

  8. 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.)

  9. 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

  10. Metal hydride and pyrophoric fuel additives for dicyclopentadiene based hybrid propellants

    Science.gov (United States)

    Shark, Steven C.

    The purpose of this study is to investigate the use of reactive energetic fuel additives that have the potential to increase the combustion performance of hybrid rocket propellants in terms of solid fuel regression rate and combustion efficiency. Additives that can augment the combustion flame zone in a hybrid rocket motor by means of increased energy feedback to the fuel grain surface are of great interest. Metal hydrides have large volumetric hydrogen densities, which gives these materials high performance potential as fuel additives in terms of specifc impulse. The excess hydrogen and corresponding base metal may also cause an increase in the hybrid rocket solid fuel regression rate. Pyrophoric additives also have potential to increase the solid fuel regression rate by reacting more readily near the burning fuel surface providing rapid energy feedback. An experimental performance evaluation of metal hydride fuel additives for hybrid rocket motor propulsion systems is examined in this study. Hypergolic ignition droplet tests and an accelerated aging study revealed the protection capabilities of Dicyclopentadiene (DCPD) as a fuel binder, and the ability for unaided ignition. Static hybrid rocket motor experiments were conducted using DCPD as the fuel. Sodium borohydride (NabH4) and aluminum hydride (AlH3) were examined as fuel additives. Ninety percent rocket grade hydrogen peroxide (RGHP) was used as the oxidizer. In this study, the sensitivity of solid fuel regression rate and characteristic velocity (C*) efficiency to total fuel grain port mass flux and particle loading is examined. These results were compared to HTPB combustion performance as a baseline. Chamber pressure histories revealed steady motor operation in most tests, with reduced ignition delays when using NabH4 as a fuel additive. The addition of NabH4 and AlH3 produced up to a 47% and 85% increase in regression rate over neat DCPD, respectively. For all test conditions examined C* efficiency ranges

  11. Design of Hydrogen Storage Alloys/Nanoporous Metals Hybrid Electrodes for Nickel-Metal Hydride Batteries

    Science.gov (United States)

    Li, M. M.; Yang, C. C.; Wang, C. C.; Wen, Z.; Zhu, Y. F.; Zhao, M.; Li, J. C.; Zheng, W. T.; Lian, J. S.; Jiang, Q.

    2016-06-01

    Nickel metal hydride (Ni-MH) batteries have demonstrated key technology advantages for applications in new-energy vehicles, which play an important role in reducing greenhouse gas emissions and the world’s dependence on fossil fuels. However, the poor high-rate dischargeability of the negative electrode materials—hydrogen storage alloys (HSAs) limits applications of Ni-MH batteries in high-power fields due to large polarization. Here we design a hybrid electrode by integrating HSAs with a current collector of three-dimensional bicontinuous nanoporous Ni. The electrode shows enhanced high-rate dischargeability with the capacity retention rate reaching 44.6% at a discharge current density of 3000 mA g‑1, which is 2.4 times that of bare HSAs (18.8%). Such a unique hybrid architecture not only enhances charge transfer between nanoporous Ni and HSAs, but also facilitates rapid diffusion of hydrogen atoms in HSAs. The developed HSAs/nanoporous metals hybrid structures exhibit great potential to be candidates as electrodes in high-performance Ni-MH batteries towards applications in new-energy vehicles.

  12. Bismuth determination in environmental samples by hydride generation-electrothermal atomic absorption spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Moscoso-Perez, Carmen; Moreda-Pineiro, Jorge; Lopez-Mahia, Purificacion; Muniategui-Lorenzo, Soledad; Fernandez-Fernandez, Esther; Prada-Rodriguez, Dario [Department of Analytical Chemistry, Faculty of Sciences, University of A Coruna, Campus da Zapateira s/n, E-15071, A Coruna (Spain)

    2003-12-04

    A hydride generation procedure, via flow injection, coupled to electrothermal atomic absorption spectrometry was optimised for Bi determination in sea water and hot-spring water and acid extracts from coal, coal fly ash and slag samples. The effects of several variables such as hydrochloric acid and sodium tetrahydroborate concentrations, hydrochloric acid and sodium tetrahydroborate flow rates, reaction coil length, trapping and atomisation temperatures, trapping time and the Ar flow rate have been investigated by using a 2{sup 9}*3/128 Plackett-Burman design. From these studies, certain variables (sodium tetrahydroborate concentration and trapping time) showed up as significant, and they were optimised by a 2{sup 2}+star central composite design. In addition, a study of the bismuthine trapping and atomisation efficiency from graphite tubes (GTs) permanently treated with uranium, tantalum, lanthanum oxide, niobium, beryllium oxide, chromium oxide and tantalum carbide were investigated. The results obtained were compared with those achieved by iridium and zirconium-treated GTs. The best analytical performances, with characteristic mass of 35 pg and detection limit of 70 ng l{sup -1}, were achieved by using U-treated GTs. Accuracy were checked using several reference materials: 1643d (Trace Elements in Water), TM-24 (Reference Water), GBW-07401 (Soil) and 1632c (Trace Elements in Coal)

  13. Hydride bridge in [NiFe]-hydrogenase observed by nuclear resonance vibrational spectroscopy

    Science.gov (United States)

    Ogata, Hideaki; Krämer, Tobias; Wang, Hongxin; Schilter, David; Pelmenschikov, Vladimir; van Gastel, Maurice; Neese, Frank; Rauchfuss, Thomas B.; Gee, Leland B.; Scott, Aubrey D.; Yoda, Yoshitaka; Tanaka, Yoshihito; Lubitz, Wolfgang; Cramer, Stephen P.

    2015-08-01

    The metabolism of many anaerobes relies on [NiFe]-hydrogenases, whose characterization when bound to substrates has proven non-trivial. Presented here is direct evidence for a hydride bridge in the active site of the 57Fe-labelled fully reduced Ni-R form of Desulfovibrio vulgaris Miyazaki F [NiFe]-hydrogenase. A unique `wagging' mode involving H- motion perpendicular to the Ni(μ-H)57Fe plane was studied using 57Fe-specific nuclear resonance vibrational spectroscopy and density functional theory (DFT) calculations. On Ni(μ-D)57Fe deuteride substitution, this wagging causes a characteristic perturbation of Fe-CO/CN bands. Spectra have been interpreted by comparison with Ni(μ-H/D)57Fe enzyme mimics [(dppe)Ni(μ-pdt)(μ-H/D)57Fe(CO)3]+ and DFT calculations, which collectively indicate a low-spin Ni(II)(μ-H)Fe(II) core for Ni-R, with H- binding Ni more tightly than Fe. The present methodology is also relevant to characterizing Fe-H moieties in other important natural and synthetic catalysts.

  14. Effect of lanthanum hydride on microstructures and hydrogen storage performances of 2LiNH2-MgH2 system

    Institute of Scientific and Technical Information of China (English)

    朱惜林; 韩树民; 赵鑫; 李媛; 刘宝忠

    2014-01-01

    Hydrogen storage properties of 2LiNH2-MgH2 system were improved by adding lanthanum hydride (LaH3), and the role of LaH3 in hydrogen sorption process of Li-Mg-N-H system was investigated. Temperature programmed sorption results showed that the addition of lanthanum hydride reduced the dehydriding/hydriding onset temperature of 2LiNH2-MgH2 system by at least 15 K. Moreover, A 0.053 wt.%/min average rate was determined for the hydrogen desorption of 2LiNH2-MgH2-0.05LaH3 composite, while it was only 0.035 wt.%/min for 2LiNH2-MgH2 system. Hydrogen absorption capacity increased from 1.62 wt.% to 2.12 wt.% within 200 min by adding LaH3 into 2LiNH2-MgH2 system at 383 K. In the dehydrogenation of 2LiNH2-MgH2-0.05LaH3 composite, LaH2 transferred to LaN phase, which reversed to LaH2 in the following hydrogen adsorption process. The reversible reaction of LaH2 ef-fectively promoted the hydrogen sorption of Li-Mg-N-H system. Moreover, the homogenous distribution of fine La hydride was fa-vorable to improving effect of lanthanum hydride.

  15. Trimethylsilyl-Substituted Hydroxycyclopentadienyl Ruthenium Hydrides as Benchmarks to Probe Ligand and Metal Effects on the Reactivity of Shvo Type Complexes.

    Science.gov (United States)

    Casey, Charles P; Guan, Hairong

    2012-01-01

    The bis(trimethylsilyl)-substituted hydroxycyclopentadienyl ruthenium hydride [2,5-(SiMe(3))(2)-3,4-(CH(2)OCH(2))(η(5)-C(4)COH)]Ru(CO)(2)H (10) is an efficient catalyst for hydrogenation of aldehydes and ketones. Because 10 transfers hydrogen rapidly to aldehydes and ketones and because it does not form an inactive bridging hydride during reaction, hydrogenation of aldehydes and ketones can be performed at room temperature under relatively low hydrogen pressure (3 atm); this is a significant improvement compared with previously developed Shvo type catalysts. Kinetic and (2)H NMR spectroscopic studies of the stoichiometric reduction of aldehydes and ketones by 10 established a two-step process for the hydrogen transfer: (1) rapid and reversible hydrogen bond formation between OH of 10 and the oxygen of the aldehyde or ketone, (2) followed by slow transfer of both proton and hydride from 10 to the aldehyde or ketone. The stoichiometric and catalytic activities of complex 10 are compared to those of other Shvo type ruthenium hydrides and related iron hydrides. PMID:23087535

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

    Science.gov (United States)

    Bhushan, Bharat; Halasz, Annamaria; Hawari, Jalal

    2005-12-01

    A dehydrogenase from Clostridium sp. EDB2 and a diaphorase from Clostridium kluyveri were reacted with CL-20 to gain insights into the enzyme-catalyzed hydride transfer to CL-20, and the enzyme's stereo-specificity for either pro-R or pro-S hydrogens of NAD(P)H. Both enzymes biotransformed CL-20 at rates of 18.5 and 24nmol/h/mg protein, using NADH and NADPH as hydride-source, respectively, to produce a N-denitrohydrogenated product with a molecular weight of 393Da. In enzyme kinetics studies using reduced deuterated pyridine nucleotides, we found a kinetic deuterium isotopic effect of 2-fold on CL-20 biotransformation rate using dehydrogenase enzyme against (R)NADD as a hydride-source compared to either (S)NADD or NADH. Whereas, in case of diaphorase, the kinetic deuterium isotopic effect of about 1.5-fold was observed on CL-20 biotransformation rate using (R)NADPD as hydride-source. In a comparative study with LC-MS, using deuterated and non-deuterated NAD(P)H, we found a positive mass-shift of 1Da in the N-denitrohydrogenated product suggesting the involvement of a deuteride (D(-)) transfer from NAD(P)D. The present study thus revealed that both dehydrogenase and diaphorase enzymes from the two Clostridium species catalyzed a hydride transfer to CL-20 and showed stereo-specificity for pro-R hydrogen of NAD(P)H. PMID:16225844

  17. Synthesis and properties of the Mg{sub 2}Ni{sub 0.5}Co{sub 0.5}H{sub 4.4} hydride

    Energy Technology Data Exchange (ETDEWEB)

    Verbovytskyy, Yu. [Physico-Mechanical Institute, NAS of Ukraine, 5 Naukova str., 79601 Lviv (Ukraine); Zhang, J.; Cuevas, F.; Paul-Boncour, V. [Institut de Chimie et des Materiaux de Paris Est, CMTR, UMR 7182, CNRS-UPEC, 2-8 rue H. Dunant, 94320 Thiais (France); Zavaliy, I., E-mail: zavaliy@ipm.lviv.ua [Physico-Mechanical Institute, NAS of Ukraine, 5 Naukova str., 79601 Lviv (Ukraine)

    2015-10-05

    Graphical abstract: Crystal structure of the Mg{sub 2}Ni{sub 0.5}Co{sub 0.5}H{sub 4.4} hydride. - Highlights: • Preparation of the Mg{sub 2}Ni{sub 0.5}Co{sub 0.5}H{sub 4.4} hydride by reactive ball milling. • Crystal structure determination by X-ray powder diffraction. • Electrochemical studies of the ball milled MH/Ni electrodes. - Abstract: The Mg{sub 2}Ni{sub 0.5}Co{sub 0.5}H{sub 4.4} hydride with a grain size of 16 nm was prepared by reactive ball milling. Its crystal structure was studied by X-ray powder diffraction. A tetragonal Mg{sub 2}CoH{sub 5} structure type was suggested for the obtained hydride. The decomposition temperature of the Mg{sub 2}Ni{sub 0.5}Co{sub 0.5}H{sub 4.4} phase was observed at 213 °C. Electrochemical measurements as negative electrode of Ni–MH battery were also performed. Significant improvements can be made by ball-milling the hydride with nickel powder.

  18. Hydriding and dehydriding rates and hydrogen-storage capacity of Mg–14Ni–3Fe2O3–3Ti prepared by reactive mechanical grinding

    Indian Academy of Sciences (India)

    Myoung Youp Song; Young Jun Kwak; Hye Ryoung Park; Byoung-Goan Kim

    2013-08-01

    The magnesium prepared by mechanical grinding under H2 (reactive mechanical grinding) with transition elements or oxides showed relatively high hydriding and dehydriding rates when the content of additives was about 20 wt%. Ni (expected to increase hydriding and dehydriding rates) was chosen as transition element to be added. Fe2O3 (expected to increase hydriding rate) was selected as an oxide to be added. Ti was also selected since, it was considered to increase the hydriding and dehydriding rates by forming Ti hydride. A sample, Mg–14Ni–3Fe2O3–3Ti, was prepared by reactive mechanical grinding and its hydrogen storage properties were investigated. This sample absorbed 4.02 wt% H for 5 min, 4.15 wt% H for 10 min and 4.42 wt% H for 60 min at = 2. It desorbed 2.46 wt% H for 10 min, 3.98 wt% H for 30 min and 4.20 wt% H for 60 min at = 2.

  19. Spectroscopic characterization of the key catalytic intermediate Ni-C in the O2-tolerant [NiFe] hydrogenase I from Aquifex aeolicus: evidence of a weakly bound hydride.

    Science.gov (United States)

    Pandelia, Maria-Eirini; Infossi, Pascale; Stein, Matthias; Giudici-Orticoni, Marie-Thérèse; Lubitz, Wolfgang

    2012-01-21

    Ni-C in the O(2)-tolerant hydrogenase I from Aquifex aeolicus binds a hydride weaker than that in O(2)-sensitive hydrogenases. This is in line with the enhanced light-sensitivity of Ni-C, greater lability of the hydride complex and increased catalytic redox potentials relevant to bio-H(2) oxidation. PMID:22143669

  20. Metal ion-catalyzed cycloaddition vs hydride transfer reactions of NADH analogues with p-benzoquinones.

    Science.gov (United States)

    Fukuzumi, S; Fujii, Y; Suenobu, T

    2001-10-24

    1-Benzyl-4-tert-butyl-1,4-dihydronicotinamide (t-BuBNAH) reacts efficiently with p-benzoquinone (Q) to yield a [2+3] cycloadduct (1) in the presence of Sc(OTf)(3) (OTf = OSO(2)CF(3)) in deaerated acetonitrile (MeCN) at room temperature, while no reaction occurs in the absence of Sc(3+). The crystal structure of 1 has been determined by the X-ray crystal analysis. When t-BuBNAH is replaced by 1-benzyl-1,4-dihydronicotinamide (BNAH), the Sc(3+)-catalyzed cycloaddition reaction of BNAH with Q also occurs to yield the [2+3] cycloadduct. Sc(3+) forms 1:4 complexes with t-BuBNAH and BNAH in MeCN, whereas there is no interaction between Sc(3+) and Q. The observed second-order rate constant (k(obs)) shows a first-order dependence on [Sc(3+)] at low concentrations and a second-order dependence at higher concentrations. The first-order and the second-order dependence of the rate constant (k(et)) on [Sc(3+)] was also observed for the Sc(3+)-promoted electron transfer from CoTPP (TPP = tetraphenylporphyrin dianion) to Q. Such dependence of k(et) on [Sc(3+)] is ascribed to formation of 1:1 and 1:2 complexes between Q(*)(-) and Sc(3+) at the low and high concentrations of Sc(3+), respectively, which results in acceleration of the rate of electron transfer. The formation constants for the 1:2 complex (K(2)) between the radical anions of a series of p-benzoquinone derivatives (X-Q(*)(-)) and Sc(3+) are determined from the dependence of k(et) on [Sc(3+)]. The K(2) values agree well with those determined from the dependence of k(obs) on [Sc(3+)] for the Sc(3+)-catalyzed addition reaction of t-BuBNAH and BNAH with X-Q. Such an agreement together with the absence of the deuterium kinetic isotope effects indicates that the addition proceeds via the Sc(3+)-promoted electron transfer from t-BuBNAH and BNAH to Q. When Sc(OTf)(3) is replaced by weaker Lewis acids such as Lu(OTf)(3), Y(OTf)(3), and Mg(ClO(4))(2), the hydride transfer reaction from BNAH to Q also occurs besides the