Cyclopentadiene-mediated hydride transfer from rhodium complexes.

PubMed

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

2016-07-12

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

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

PubMed

Yeşiller, Semira Unal; Yalçın, Serife

2013-04-03

A laser induced breakdown spectrometry hyphenated with on-line continuous flow hydride generation sample introduction system, HG-LIBS, has been used for the determination of arsenic, antimony, lead and germanium in aqueous environments. Optimum chemical and instrumental parameters governing chemical hydride generation, laser plasma formation and detection were investigated for each element under argon and nitrogen atmosphere. Arsenic, antimony and germanium have presented strong enhancement in signal strength under argon atmosphere while lead has shown no sensitivity to ambient gas type. Detection limits of 1.1 mg L(-1), 1.0 mg L(-1), 1.3 mg L(-1) and 0.2 mg L(-1) were obtained for As, Sb, Pb and Ge, respectively. Up to 77 times enhancement in detection limit of Pb were obtained, compared to the result obtained from the direct analysis of liquids by LIBS. Applicability of the technique to real water samples was tested through spiking experiments and recoveries higher than 80% were obtained. Results demonstrate that, HG-LIBS approach is suitable for quantitative analysis of toxic elements and sufficiently fast for real time continuous monitoring in aqueous environments. Copyright © 2013 Elsevier B.V. All rights reserved.

METHOD OF FABRICATING A URANIUM-ZIRCONIUM HYDRIDE REACTOR CORE

DOEpatents

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

1960-03-22

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

Rare earth element recycling from waste nickel-metal hydride batteries.

PubMed

Yang, Xiuli; Zhang, Junwei; Fang, Xihui

2014-08-30

With an increase in number of waste nickel-metal hydride batteries, and because of the importance of rare earth elements, the recycling of rare earth elements is becoming increasingly important. In this paper, we investigate the effects of temperature, hydrochloric acid concentration, and leaching time to optimize leaching conditions and determine leach kinetics. The results indicate that an increase in temperature, hydrochloric acid concentration, and leaching time enhance the leaching rate of rare earth elements. A maximum rare earth elements recovery of 95.16% was achieved at optimal leaching conditions of 70°C, solid/liquid ratio of 1:10, 20% hydrochloric acid concentration, -74μm particle size, and 100min leaching time. The experimental data were best fitted by a chemical reaction-controlled model. The activation energy was 43.98kJ/mol and the reaction order for hydrochloric acid concentration was 0.64. The kinetic equation for the leaching process was found to be: 1-(1-x)(1/3)=A/ρr0[HCl](0.64)exp-439,8008.314Tt. After leaching and filtration, by adding saturated oxalic solution to the filtrate, rare earth element oxalates were obtained. After removing impurities by adding ammonia, filtering, washing with dilute hydrochloric acid, and calcining at 810°C, a final product of 99% pure rare earth oxides was obtained. Copyright © 2014 Elsevier B.V. All rights reserved.

Edge profiles in K shell photoabsorption spectra of gaseous hydrides of 3p elements and homologues

NASA Astrophysics Data System (ADS)

Hauko, R.; Gomilšek, J. Padežnik; Kodre, A.; Arčon, I.; Aquilanti, G.

2017-10-01

Photoabsorption spectra of gaseous hydrides of 3p elements (PH3, H2S, HCl) are measured in the energy region of photoexcitations pertaining to K edge. The analysis of the edge profile is extended to hydrides of 4p series (GeH4, AsH3, H2Se, HBr) from an earlier experiment, and to published spectra of 2p hydrides (CH4, NH3, H2O, HF) and noble gases Ar, Kr and Ne and SiH4. The edge profiles are modelled with a linear combination of lorentzian components, describing excitations to individual bound states and to continuum. Transition energies and probabilities are also calculated in the non-relativistic molecular model of the ORCA code, in good agreement with the experiment. Edge profiles in the heavier homologues are closely similar, the symmetry of the molecule governs the transitions to the lowest unoccupied orbitals. In 2p series the effect of the strong nuclear potential prevails. Transitions to higher, atomic-like levels remain very much the same as in free atoms.

Hydrides and Borohydrides of Light Elements

DTIC Science & Technology

1947-12-04

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

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

NASA Astrophysics Data System (ADS)

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

2007-03-01

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

Rechargeable metal hydrides for spacecraft application

NASA Technical Reports Server (NTRS)

Perry, J. L.

1988-01-01

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

Achieving 100% Efficient Postcolumn Hydride Generation for As Speciation Analysis by Atomic Fluorescence Spectrometry.

PubMed

Marschner, Karel; Musil, Stanislav; Dědina, Jiří

2016-04-05

An experimental setup consisting of a flow injection hydride generator coupled to an atomic fluorescence spectrometer was optimized in order to generate arsanes from tri- and pentavalent inorganic arsenic species (iAs(III), iAs(V)), monomethylarsonic acid (MAs(V)), and dimethylarsinic acid (DMAs(V)) with 100% efficiency with the use of only HCl and NaBH4 as the reagents. The optimal concentration of HCl was 2 mol L(-1); the optimal concentration of NaBH4 was 2.5% (m/v), and the volume of the reaction coil was 8.9 mL. To prevent excessive signal noise due to fluctuations of hydride supply to an atomizer, a new design of a gas-liquid separator was implemented. The optimized experimental setup was subsequently interfaced to HPLC and employed for speciation analysis of arsenic. Two chromatography columns were tested: (i) ion-pair chromatography and (ii) ion exchange chromatography. The latter offered much better results for human urine samples without a need for sample dilution. Due to the equal hydride generation efficiency (and thus the sensitivities) of all As species, a single species standardization by DMAs(V) standard was feasible. The limits of detection for iAs(III), iAs(V), MAs(V), and DMAs(V) were 40, 97, 57, and 55 pg mL(-1), respectively. Accuracy of the method was tested by the analysis of the standard reference material (human urine NIST 2669), and the method was also verified by the comparative analyses of human urine samples collected from five individuals with an independent reference method.

Hydride Generation for Headspace Solid-Phase Extraction with CdTe Quantum Dots Immobilized on Paper for Sensitive Visual Detection of Selenium.

PubMed

Huang, Ke; Xu, Kailai; Zhu, Wei; Yang, Lu; Hou, Xiandeng; Zheng, Chengbin

2016-01-05

A low-cost, simple, and highly selective analytical method was developed for sensitive visual detection of selenium in human urine both outdoors and at home, by coupling hydride generation with headspace solid-phase extraction using quantum dots (QDs) immobilized on paper. The visible fluorescence from the CdTe QDs immobilized on paper was quenched by H2Se from hydride generation reaction and headspace solid-phase extraction. The potential mechanism was investigated by using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) as well as Density Functional Theory (DFT). Potential interferences from coexisting ions, particularly Ag(+), Cu(2+), and Zn(2+), were eliminated. The selectivity was significantly increased because the selenium hydride was effectively separated from sample matrices by hydride generation. Moreover, due to the high sampling efficiency of hydride generation and headspace solid phase extraction, the sensitivity and the limit of detection (LOD) were significantly improved compared to conventional methods. A LOD of 0.1 μg L(-1) and a relative standard deviation (RSD, n = 7) of 2.4% at a concentration of 20 μg L(-1) were obtained when using a commercial spectrofluorometer as the detector. Furthermore, a visual assay based on the proposed method was developed for the detection of Se, 5 μg L(-1) of selenium in urine can be discriminated from the blank solution with the naked eye. The proposed method was validated by analysis of certified reference materials and human urine samples with satisfactory results.

A nickel metal hydride battery for electric vehicles

NASA Astrophysics Data System (ADS)

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

1993-04-01

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

Thermodynamic Hydricity of Transition Metal Hydrides

DOE PAGES

Wiedner, Eric S.; Chambers, Matthew B.; Pitman, Catherine L.; ...

2016-08-02

Transition metal hydrides play a critical role in stoichiometric and catalytic transformations. Knowledge of free energies for cleaving metal hydride bonds enables the prediction of chemical reactivity, such as for the bond-forming and bondbreaking events that occur in a catalytic reaction. Thermodynamic hydricity is the free energy required to cleave an M-H bond to generate a hydride ion (H -). Three primary methods have been developed for hydricity determination: the hydride transfer method establishes hydride transfer equilibrium with a hydride donor/acceptor pair of known hydricity, the H 2 heterolysis method involves measuring the equilibrium of heterolytic cleavage of H 2more » in the presence of a base, and the potential-pK a method considers stepwise transfer of a proton and two electrons to give a net hydride transfer. Using these methods, over 100 thermodynamic hydricity values for transition metal hydrides have been determined in acetonitrile or water. In acetonitrile, the hydricity of metal hydrides spans a range of more than 50 kcal/mol. Finally, methods for using hydricity values to predict chemical reactivity are also discussed, including organic transformations, the reduction of CO 2, and the production and oxidation of hydrogen.« less

The effect of stress state on zirconium hydride reorientation

NASA Astrophysics Data System (ADS)

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

Process for massively hydriding zirconium--uranium fuel elements

DOEpatents

Katz, N.H.

1973-12-01

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

Activated aluminum hydride hydrogen storage compositions and uses thereof

DOEpatents

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

2010-11-23

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

Determination of lead by hydride generation inductively coupled plasma mass spectrometry (HG-ICP-MS): on-line generation of plumbane using potassium hexacyanomanganate(III)

PubMed Central

Yilmaz, Vedat; Arslan, Zikri; Rose, LaKeysha

2012-01-01

A hydride generation (HG) procedure has been described for determination of Pb by ICP-MS using potassium hexacyanomanganate(III), K3Mn(CN)6, as an additive to facilitate the generation of plumbane (PbH4). Potassium hexacyanomanganate(III) was prepared in acidic medium as it was unstable in water. The stability of hexacyanomanganate(III) was examined in dilute solutions of HCl, HNO3 and H2SO4. The solutions prepared in 1% v/v/ H2SO4 were found to be stable for over a period of 24 h. The least suitable medium was 1% v/v HNO3. For generation of plumbane, acidic hexacyanomanganate(III) and sample solutions were mixed online along a 5-cm long tygon tubing (1.14 mm i.d.) and then reacted with 2% m/v sodium borohydride (NaBH4). A concentration of 0.5% m/v K3Mn(CN)6 facilitated the generation of PbH4 remarkably. In comparison to H2SO4, HCl provided broader working range for which optimum concentration was 1% v/v. No significant interferences were noted from transition metals and hydride forming elements, up to 0.5 μg mL−1 levels, except Cu which depressed the signals severely. The depressive effects in the presence of 0.1 μg mL−1 Cu were alleviated by increasing the concentration of K3Mn(CN)6 to 2% m/v. Under these conditions, the sensitivity was enhanced by a factor of at least 42 to 48. The detection limit (3s) was 0.008 μg L−1 for 208Pb isotope. Average signal-to-noise ratio (S/N) ranged between 18 and 20 for 1.0 μg mL−1 Pb solution. The accuracy of the method was verified by analysis of several certified reference materials, including Nearshore seawater (CASS-4), Bone ash (SRM 1400), and Mussel tissue (SRM 2976). The procedure was also successfully applied to the determination of Pb in coastal seawater samples by ICP-MS. PMID:23312310

Pyrometallurgical Extraction of Valuable Elements in Ni-Metal Hydride Battery Electrode Materials

NASA Astrophysics Data System (ADS)

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.

Application of metal hydride paper to simple pressure generator for use in soft actuator systems.

PubMed

Ino, Shuichi; Sakaki, Kouji; Hosono, Minako; Doi, Kouki; Shimada, Shigenobu; Chikai, Manabu

2015-01-01

Metal hydride (MH) actuators have a simple structure and a number of features that make them attractive for use in rehabilitation engineering and assistive technology. The MH actuator provides a high power-to-weight ratio, high-strain actuation, human-compatible softness, and noiseless operation, while being environmentally benign. On the other hand, there remain technical challenges to be overcome to improve the MH actuator regarding its speed of operation and energy efficiency, given the low heat conductivity of the MH powder that is used as the pressure generator for soft actuation. To overcome the issues of low heat conductivity and the handling of MH powder, we developed an MH paper, which is a special paper incorporating MH powder and carbon fiber, for use as a new pressure-generating element for a soft MH actuator system. In addition, the basic properties and structure of the proposed MH paper were investigated through scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and several thermodynamic experiments. The results of these experiments showed that the hydrogen absorption and desorption rates of the MH paper were significantly higher than those of the MH powder around room temperature.

Determination of arsenic and selenium by hydride generation and headspace solid phase microextraction coupled with optical emission spectrometry

NASA Astrophysics Data System (ADS)

Tyburska, Anna; Jankowski, Krzysztof; Rodzik, Agnieszka

2011-07-01

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 - 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.

Storage, generation, and use of hydrogen

DOEpatents

McClaine, Andrew W.; Rolfe, Jonathan L.; Larsen, Christopher A.; Konduri, Ravi K.

2006-05-30

A composition comprising a carrier liquid; a dispersant; and a chemical hydride. The composition can be used in a hydrogen generator to generate hydrogen for use, e.g., as a fuel. A regenerator recovers elemental metal from byproducts of the hydrogen generation process.

Method of generating hydrogen-storing hydride complexes

DOEpatents

None, None

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.

Sodium-based hydrides for thermal energy applications

NASA Astrophysics Data System (ADS)

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

2016-04-01

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

Simultaneous quantitative analysis of arsenic, bismuth, selenium, and tellurium in soil samples using multi-channel hydride-generation atomic fluorescence spectrometry.

PubMed

Wang, Fang; Zhang, Gai

2011-03-01

The basic principles and the application of hydride-generation multi-channel atomic fluorescence spectrometry (HG-MC-AFS) in soil analysis are described. It is generally understood that only one or two elements can be simultaneously detected by commonly used one- or two-channel HG-AFS. In this work, a new sample-sensitive and effective method for the analysis of arsenic, bismuth, tellurium, and selenium in soil samples by simultaneous detection using HG-MC-AFS was developed. The method detection limits for arsenic, bismuth, tellurium, and selenium are 0.19 μg/g, 0.10 μg/g, 0.11 μg/g, and 0.08 μg/g, respectively. This method was successfully applied to the simultaneous determination of arsenic, bismuth, tellurium, and selenium in soil samples.

Hydrogen storage in the form of metal hydrides

NASA Technical Reports Server (NTRS)

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

1984-01-01

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

Hydriding process

DOEpatents

Raymond, J.W.; Taketani, H.

1973-12-01

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

Fundamental experiments on hydride reorientation in zircaloy

NASA Astrophysics Data System (ADS)

Colas, Kimberly B.

remain constant in the tensile direction during the second precipitation regime. This could be due to the fact that the face of reoriented hydride platelet is in compression once these platelets have grown to a sufficient size. The second goal of this study was to perform a spatially resolved study of the effect of a stress concentration such as a notch or a crack on hydride reorientation. Using SEM and image analysis, it was found that a sharp crack induces a different hydride microstructure than a blunt notch. In the case of sharp crack, hydrides are more localized and align more with the defect than for blunt notches. The hydride connectivity also increases close to a stress concentration which will assist in crack propagation during DHC. Using TEM, the microstructure of hydrides grown near crack tips were observed to be similar to that of circumferential hydrides grown in the bulk. The orientation relationship studied with SEM and micro-X-ray diffraction was found to be in most cases δ(111)// α(0002) for hydrides grown both near and far from stress concentrations. Using the same micro-X-ray diffraction technique local hydride and matrix elastic strains were measured and observed to vary significantly from grain to grain. It was however observed that hydrides grown close to the stress concentration are in tension in the face of the platelet, similar to reoriented hydrides, while those grown far from the stress concentration are in tension, similar to circumferential hydrides. The orders of magnitude of the measured strains in the hydrides and the zirconium matrix compared well to those predicted by finite element models. This study shows that it is possible to study hydride dissolution and precipitation in-situ using time-dependent techniques. It was found that the precipitation temperature is lowered by hydride reorientation. The evolution of hydride strains during precipitation was found to be different for unstressed, stressed and reoriented hydrides. The

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

2016-12-20

Uranium hydride corrosion is of great interest to the nuclear industry. Uranium reacts with water and/or hydrogen to form uranium hydride which adversely affects material performance. Hydride nucleation is influenced by thermal history, mechanical defects, oxide thickness, and chemical defects. Information has been gathered from past hydride experiments to formulate a uranium hydride model to be used in a Canned Subassembly (CSA) lifetime prediction model. This multi-scale computer modeling effort started in FY’13, and the fourth generation model is now complete. Additional high-resolution experiments will be run to further test the model.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Breault, R.W.; Rolfe, J.

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, Thermomore » 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.« less

Hydride compositions

DOEpatents

Lee, Myung, W.

1994-01-01

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

Hydride compositions

DOEpatents

Lee, Myung W.

1995-01-01

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

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

NASA Astrophysics Data System (ADS)

Zhou, Chengshang

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

An elasto-plastic fracture mechanics based model for assessment of hydride embrittlement in zircaloy cladding tubes

NASA Astrophysics Data System (ADS)

Nilsson, Karl-Fredrik; Jakšić, Nikola; Vokál, Vratko

2010-01-01

This paper describes a finite element based fracture mechanics model to assess how hydrides affect the integrity of zircaloy cladding tubes. The hydrides are assumed to fracture at a low load whereas the propagation of the fractured hydrides in the matrix material and failure of the tube is controlled by non-linear fracture mechanics and plastic collapse of the ligaments between the hydrides. The paper quantifies the relative importance of hydride geometrical parameters such as size, orientation and location of individual hydrides and interaction between adjacent hydrides. The paper also presents analyses for some different and representative multi-hydride configurations. The model is adaptable to general and complex crack configurations and can therefore be used to assess realistic hydride configurations. The mechanism of cladding failure is by plastic collapse of ligaments between interacting fractured hydrides. The results show that the integrity can be drastically reduced when several radial hydrides form continuous patterns.

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

PubMed

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

2018-01-25

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

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

PubMed

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

2014-01-01

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

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

PubMed

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. Copyright © 2015 Elsevier B.V. All rights

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

NASA Astrophysics Data System (ADS)

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.

Speciation analysis of arsenic in biological matrices by automated hydride generation-cryotrapping-atomic absorption spectrometry with multiple microflame quartz tube atomizer (multiatomizer).

EPA Science Inventory

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...

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

NASA Astrophysics Data System (ADS)

Matusiewicz, Henryk; Krawczyk, Magdalena

2007-03-01

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 2Te 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 arrangements (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 σ), was 0.9 ng mL - 1 for Te. For a 2 min in situ pre-concentration 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 designs studied include slotted tube, single silica tube and integrated atom trap-cooled atom traps. 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.

Hydrogen, lithium, and lithium hydride production

DOEpatents

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

2017-06-20

A method is provided for extracting hydrogen from lithium hydride. The method includes (a) heating lithium hydride to form liquid-phase lithium hydride; (b) extracting hydrogen from the liquid-phase lithium hydride, leaving residual liquid-phase lithium metal; (c) hydriding the residual liquid-phase lithium metal to form refined lithium hydride; and repeating steps (a) and (b) on the refined lithium hydride.

Studies of hydride formation and superconductivity in hydrides of alloys Th-M /M = La, Y, Ce, Zr and Bi/

NASA Technical Reports Server (NTRS)

Oesterreicher, H.; Clinton, J.; Misroch, M.

1977-01-01

In order to gain a better insight into both the unusual composition of ThH15 and its superconductivity, an experimental study was conducted to assess the influence of partial replacement of Th in Th4H15 by elements which allow for a systematic alteration of spatial and electronic effects. For this purpose, substituent elements with the same number of valence electrons (4) but of smaller size (Zr) as well as elements with a smaller number of valence electrons (3) and either larger (La) or smaller size (Y) were selected. A few data with Ce and Bi as substituent atoms are also included. The matrix alloys for hydriding were obtained by induction melting under Ar in water-cooled Cu boats. Superconducting transition temperatures are found to decrease on substitution for Th in Th4H15. Hydrides derived from LaH3 by substitution for La by Th do not become superconducting. It is suggested that superconductivity in Th4H15 is connected with a deviation from the exact stoichiometry of Th4H15. A model of unsatisfied valencies may be of more general validity in predicting superconductivity.

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

PubMed

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

2014-03-24

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

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

NASA Astrophysics Data System (ADS)

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

2014-03-01

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

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

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

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Daniel A. Mosher; Xia Tang; Ronald J. Brown

2007-07-27

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

Rapid sequential determination of arsenic and selenium in waters and plant digests by hydride generation inductively coupled plasma-mass spectrometry

NASA Astrophysics Data System (ADS)

Menegário, Amauri A.; Giné, Maria Fernanda

2000-04-01

A synchronised flow system with hydride generation coupled to ICP-MS is proposed for the sequential determination of As and Se in natural waters and plant digests. The alternated mixing of the sample solution with thiourea or HCl for the determination of As or Se under optimized conditions was achieved using a flow commutator before the reaction with NaBH 4. The on-line addition of thiourea promoted the quantitative reduction of As(V) to As(III), thus enhancing sensitivity and precision. The selenium pre-reduction from Se(VI) to Se(IV) was produced by heating the sample with HCl, and the hydride generation was performed in 4 mol l -1 HCl, thus avoiding interference from thiourea. The system allowed the analysis of 20 samples h -1 with LOD values of 0.02 μg l -1 As and 0.03 μg l -1 Se. Results were in agreement with the certified values at the 95% confidence level for reference waters from the Canadian National Water Research Institute and plant samples from the National Institute of Standards and Technology (NIST).

A COMPARISON OF URINARY ARSENIC SPECIATION VIA DIRECT NEBULIZATION AND ON-LINE PHOTOOXIDATION-HYDRIDE GENERATION WITH DETECTION BY INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY

EPA Science Inventory

Arsenic speciation continues to be important in assessing human and environmental exposure risk. Urinary arsenic analysis provides information on recent arsenic exposure. In this study, two sample introduction pathways: direct nebulization (DN) and hydride generation (HG) were ut...

Oriented xenon hydride molecules in the gas phase

NASA Astrophysics Data System (ADS)

Buck, Udo; Fárník, Michal

The production of the xenon hydride molecules HXeX with X = I and Cl in the gas phase is reviewed. These molecules are generated by the photolysis of the hydrogen halide HI and HCl molecules on the surface of large xenon Xen clusters. Molecular dynamics simulations show that the flexible H atoms react with the heavy XeX moiety and form the desired molecules with nearly no rotational motion. They are observed by photodissociation with subsequent detection of the kinetic energy of the H atom fragment. During the generating process, the cluster starts to evaporate and the hydride molecule is left essentially free. For further discrimination against the H atom fragments from HX, the HXeX molecules are oriented in a combined pulsed laser field and a weak electrostatic field. The three topics which represent the background of our experiments are briefly reviewed: the nature and generation of rare gas hydrides, the alignment and orientation of molecules in electric fields, and the photodissociation of selected molecules in rare gas clusters. The conditions for detecting them in the gas phase are discussed. This is the trade off between the stability, which requires high electron affinity, and the conditions for orientation, which necessitate large polarizability anisotropies and dipole moments. Finally the prospects of detecting other classes of molecules are discussed.

ORNL Interim Progress Report on Hydride Reorientation CIRFT Tests

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

A systematic study of H. B. Robinson (HBR) high burnup spent nuclear fuel (SNF) vibration integrity was performed in Phase I project under simulated transportation environments, using the Cyclic Integrated Reversible-Bending Fatigue Tester (CIRFT) hot cell testing technology developed at Oak Ridge National Laboratory in 2013–14. The data analysis on the as-irradiated HBR SNF rods demonstrated that the load amplitude is the dominant factor that controls the fatigue life of bending rods. However, previous studies have shown that the hydrogen content and hydride morphology has an important effect on zirconium alloy mechanical properties. To address the effect of radial hydridesmore » in SNF rods, in Phase II a test procedure was developed to simulate the effects of elevated temperatures, pressures, and stresses during transfer-drying operations. Pressurized and sealed fuel segments were heated to the target temperature for a preset hold time and slow-cooled at a controlled rate. The procedure was applied to both non-irradiated/prehydrided and high-burnup Zircaloy-4 fueled cladding segments using the Nuclear Regulatory Commission-recommended 400°C maximum temperature limit at various cooling rates. Before testing high-burnup cladding, four out-of-cell tests were conducted to optimize the hydride reorientation (R) test condition with pre-hydride Zircaloy-4 cladding, which has the same geometry as the high burnup fuel samples. Test HR-HBR#1 was conducted at the maximum hoop stress of 145 MPa, at a 400°C maximum temperature and a 5°C/h cooling rate. On the other hand, thermal cycling was performed for tests HR-HBR#2, HR-HBR#3, and HR-HBR#4 to generate more radial hydrides. It is clear that thermal cycling increases the ratio of the radial hydride to circumferential hydrides. The internal pressure also has a significant effect on the radial hydride morphology. This report describes a procedure and experimental results of the four out-of-cell hydride reorientation

[Indirect determination of rare earth elements in Chinese herbal medicines by hydride generation-atomic fluorescence spectrometry].

PubMed

Zeng, Chao; Lu, Jian-Ping; Xue, Min-Hua; Tan, Fang-Wei; Wu, Xiao-Yan

2014-07-01

Based on their similarity in chemical properties, rare earth elements were able to form stable coordinated compounds with arsenazo III which were extractable into butanol in the presence of diphenylguanidine. The butanol was removed under reduced pressure distillation; the residue was dissolved with diluted hydrochloric acid. As was released with the assistance of KMnO4 and determined by hydrogen generation-atomic fluorescence spectrometry in terms of rare earth elements. When cesium sulfate worked as standard solution, extraction conditions, KMnO4 amount, distillation temperature, arsenazo III amount, interfering ions, etc were optimized. The accuracy and precision of the method were validated using national standard certified materials, showing a good agreement. Under optimum condition, the linear relationship located in 0.2-25 microg x mL(-1) and detection limit was 0.44 microg x mL(-1). After the herbal samples were digested with nitric acid and hydrogen peroxide, the rare earth elements were determined by this method, showing satisfactory results with relative standard deviation of 1.3%-2.5%, and recoveries of 94.4%-106.0%. The method showed the merits of convenience and rapidness, simple instrumentation and high accuracy. With the rare earths enriched into organic phase, the separation of analytes from matrix was accomplished, which eliminated the interference. With the residue dissolved by diluted hydrochloric acid after the solvent was removed, aqueous sample introduction eliminated the impact of organic phase on the tubing connected to pneumatic pump.

Storing energy in metal hydrides - A review of the physical metallurgy

NASA Astrophysics Data System (ADS)

Ivey, D. G.; Northwood, D. O.

1983-02-01

The properties of metal hydrides, which are significant in terms of their potential as a hydrogen storage medium, are discussed. Attention is given to bonding and electronic factors of metal hydrides, which, when combined with hydrogen, form saline, ionic, metallic, and covalent bonds, with the resultant materials being either solid, liquid, or gaseous. Metallic bonds are the most promising for hydrogen storage, and involve most of the elements of groups IIIA-VIIIA in the periodic table. An analysis of the thermodynamics and kinetics of metal hydrides is presented, noting the effects of alloy composition, crystal structure, and contaminants on the effectiveness of the materials as hydrides. Hysteresis has been found to occur when the transition pressure in a pressure-composition-temperature curve is higher for absorption than for desorption, although the actual causes for hysteresis are not understood. The AB group of intermetallics has been determined to store hydrogen at the lowest cost. Examples from tests using the AB compounds are outlined, and attempts to rectify storage requirement deficiencies by adjusting the alloy compositions are described.

High growth rate hydride vapor phase epitaxy at low temperature through use of uncracked hydrides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schulte, Kevin L.; Braun, Anna; Simon, John

We demonstrate hydride vapor phase epitaxy (HVPE) of GaAs with unusually high growth rates (RG) at low temperature and atmospheric pressure by employing a hydride-enhanced growth mechanism. Under traditional HVPE growth conditions that involve growth from Asx species, RG exhibits a strong temperature dependence due to slow kinetics at the surface, and growth temperatures >750 degrees C are required to obtain RG > 60 um/h. We demonstrate that when the group V element reaches the surface in a hydride, the kinetic barrier is dramatically reduced and surface kinetics no longer limit RG. In this regime, RG is dependent on massmore » transport of uncracked AsH3 to the surface. By controlling the AsH3 velocity and temperature profile of the reactor, which both affect the degree of AsH3 decomposition, we demonstrate tuning of RG. We achieve RG above 60 um/h at temperatures as low as 560 degrees C and up to 110 um/h at 650 degrees C. We incorporate high-RG GaAs into solar cell devices to verify that the electronic quality does not deteriorate as RG is increased. The open circuit voltage (VOC), which is a strong function of non-radiative recombination in the bulk material, exhibits negligible variance in a series of devices grown at 650 degrees C with RG = 55-110 um/h. The implications of low temperature growth for the formation of complex heterostructure devices by HVPE are discussed.« less

High growth rate hydride vapor phase epitaxy at low temperature through use of uncracked hydrides

DOE PAGES

Schulte, Kevin L.; Braun, Anna; Simon, John; ...

2018-01-22

We demonstrate hydride vapor phase epitaxy (HVPE) of GaAs with unusually high growth rates (RG) at low temperature and atmospheric pressure by employing a hydride-enhanced growth mechanism. Under traditional HVPE growth conditions that involve growth from Asx species, RG exhibits a strong temperature dependence due to slow kinetics at the surface, and growth temperatures >750 degrees C are required to obtain RG > 60 um/h. We demonstrate that when the group V element reaches the surface in a hydride, the kinetic barrier is dramatically reduced and surface kinetics no longer limit RG. In this regime, RG is dependent on massmore » transport of uncracked AsH3 to the surface. By controlling the AsH3 velocity and temperature profile of the reactor, which both affect the degree of AsH3 decomposition, we demonstrate tuning of RG. We achieve RG above 60 um/h at temperatures as low as 560 degrees C and up to 110 um/h at 650 degrees C. We incorporate high-RG GaAs into solar cell devices to verify that the electronic quality does not deteriorate as RG is increased. The open circuit voltage (VOC), which is a strong function of non-radiative recombination in the bulk material, exhibits negligible variance in a series of devices grown at 650 degrees C with RG = 55-110 um/h. The implications of low temperature growth for the formation of complex heterostructure devices by HVPE are discussed.« less

Atomic-absorption spectrochemical analysis for ultratrace elements in geological materials by hydride-forming techniques: Selenium.

PubMed

Sighinolfi, G P; Gorgoni, C

1981-03-01

A method based on hydride generation for the AAS determination of selenium at nanogram levels in geological materials is described. The sample is decomposed by aqua regia attack in a sealed Teflon bomb. After treatment with hydrochloric acid, selenium is converted into hydrogen selenide by reaction with sodium borohydride and determined by AAS. Matrix interference effects have been investigated, but though they are rarely significant, the standard-additions method is recommended. The absolute sensitivity of the method is about 2.0 ng of Se (in 10 ml of solution). Detection limits of about 5-10 ng in a 1.0-g sample have been achieved with the use of "Suprapure" reagents. The selenium content of some USGS, CRPG and ANRT reference samples is reported.

Method for preparing porous metal hydride compacts

DOEpatents

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

1981-01-01

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

Method for preparing porous metal hydride compacts

DOEpatents

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

1980-01-21

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

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

NASA Technical Reports Server (NTRS)

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

1993-01-01

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

Automatic finite element generators

NASA Technical Reports Server (NTRS)

Wang, P. S.

1984-01-01

The design and implementation of a software system for generating finite elements and related computations are described. Exact symbolic computational techniques are employed to derive strain-displacement matrices and element stiffness matrices. Methods for dealing with the excessive growth of symbolic expressions are discussed. Automatic FORTRAN code generation is described with emphasis on improving the efficiency of the resultant code.

Development of metal hydride composites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Congdon, J.W.

1992-12-01

Most of current hydride technology at Savannah River Site is based on beds of metal hydride powders; the expansion upon hydridation and the cycling results in continued breakdown into finer particles. Goal is to develop a composite which will contain the fines in a dimensionally stable matrix, for use in processes which require a stable gas flow through a hydride bed. Metal hydride composites would benefit the advanced Thermal Cycling Absorption process (hydrogen isotope separation), and the Replacement Tritium Facility (storage, pumping, compression, purification of hydrogen isotopes). These composites were fabricated by cold compaction of a mixture of metal hydridemore » granules and coarse copper powder; the porosity in the granules was introduced by means of ammonium carbonate. The composite pellets were cycled 138 times in hydrogen with the loss of LANA0.75 (LaNi{sub 4.25}Al{sub 0.75}) limited to the surface. Vacuum sintering can provide additional strength at the edges. Without a coating, the metal hydride particles exposed at the pellet surface can be removed by cycling several times in hydrogen.« less

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

NASA Astrophysics Data System (ADS)

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

Alkali Metal Cation Affinities of Anionic Main Group-Element Hydrides Across the Periodic Table.

PubMed

Boughlala, Zakaria; Fonseca Guerra, Célia; Bickelhaupt, F Matthias

2017-10-05

We have carried out an extensive exploration of gas-phase alkali metal cation affinities (AMCA) of archetypal anionic bases across the periodic system using relativistic density functional theory at ZORA-BP86/QZ4P//ZORA-BP86/TZ2P. AMCA values of all bases were computed for the lithium, sodium, potassium, rubidium and cesium cations and compared with the corresponding proton affinities (PA). One purpose of this work is to provide an intrinsically consistent set of values of the 298 K AMCAs of all anionic (XH n-1 - ) constituted by main group-element hydrides of groups 14-17 along the periods 2-6. In particular, we wish to establish the trend in affinity for a cation as the latter varies from proton to, and along, the alkali cations. Our main purpose is to understand these trends in terms of the underlying bonding mechanism using Kohn-Sham molecular orbital theory together with a quantitative bond energy decomposition analyses (EDA). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of As in tobacco by using electrochemical hydride generation at a Nafion® solid polymer electrolyte cell hyphenated with atomic fluorescence spectrometry

NASA Astrophysics Data System (ADS)

Yang, Qinghua; Gan, Wuer; Deng, Yun; Sun, Huihui

2011-11-01

In the present work, a novel solid polymer electrolyte hydride generation (SPE-HG) cell was developed. The home-made SPE-HG cell, mainly composed of three components (Nafion®117 membrane for separating and H + exchanging, a soft graphite felt cathode and a Ti mesh modified by Ir anode), was employed for detecting As by coupling to atomic fluorescence spectrometry (AFS). The H + generated by electrolysis of pure water in anode chamber transferred to cathode chamber through SPE, and immediately reacted with As 3 + to generate AsH 3. The relative mechanisms and operation conditions for hydride generation of As were investigated in detail. The developed cell employed water as an alternative of acid anolyte, with virtues of low-cost, more than 6 months lifetime and environment friendly compared with the conventional cell. Under the optimized conditions, the limit of determination of As 3 + for sample blank solution was 0.12 μg L - 1 , the RSD was 2.9% for 10 consecutive measurements of 5 μg L - 1 As 3 + standard solution. The accuracy of the method was verified by the determination of As in the reference Tea (GBW07605) and the developed method was successfully applied to determine trace amounts of As in tobacco samples with recovery from 97% to 103%.

Hydrogen /Hydride/-air secondary battery

NASA Technical Reports Server (NTRS)

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

1979-01-01

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

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

PubMed

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

2014-12-01

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

Physics of hydride fueled PWR

NASA Astrophysics Data System (ADS)

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.

Hydrogen, lithium, and lithium hydride production

DOEpatents

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

2014-03-25

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

Dimensionally stable metallic hydride composition

DOEpatents

Heung, Leung K.

1994-01-01

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

Insight into destabilization mechanism of Mg-based hydrides interstitially co-doped with nonmetals: a DFT study

NASA Astrophysics Data System (ADS)

Wu, Zhen; Zhu, Luying; Yang, Fusheng; Zhang, Zaoxiao; Nyamsi, Serge N.

2018-04-01

Mg-based metal hydride is one of the most promising materials for hydrogen energy storage. However, the high thermal stability due to strong bonding effects between the atoms limits its practical application. In order to reduce the thermal stability, a method of doping double nonmetals into Mg-based system was proposed in this study. The density functional theory (DFT) calculation results showed that the thermal stabilities of both the B-N co-doped Mg-based alloy and its hydride are reduced compared with pure Mg-based system. The relative formation enthalpies of the alloy and its hydride are 0.323 and 0.595 eV atom-1, respectively. The values are much higher than those for either singly B- or N-doped Mg-based system. The more significant destabilization by doping double nonmetal elements than single element is mainly attributed to a dual effect in weakening Mg-Ni/NiH4 bonds, caused by criss-cross interactions between B-Ni and N-Mg bonds.

Metal hydride composition and method of making

DOEpatents

Congdon, James W.

1995-01-01

A dimensionally stable hydride composition and a method for making such a composition. The composition is made by forming particles of a metal hydride into porous granules, mixing the granules with a matrix material, forming the mixture into pellets, and sintering the pellets in the absence of oxygen. The ratio of matrix material to hydride is preferably between approximately 2:1 and 4:1 by volume. The porous structure of the granules accommodates the expansion that occurs when the metal hydride particles absorb hydrogen. The porous matrix allows the flow of hydrogen therethrough to contact the hydride particles, yet supports the granules and contains the hydride fines that result from repeated absorption/desorption cycles.

Silica hydride intermediate for octadecylsilica and phenyl bonded phase preparation via heterogeneous hydrosilation in supercritical carbon dioxide.

PubMed

Scully, N M; Ashu-Arrah, B A; Nagle, A P; Omamogho, J O; O'Sullivan, G P; Friebolin, V; Dietrich, B; Albert, K; Glennon, J D

2011-04-15

Investigations into the preparation of silica hydride intermediate in supercritical carbon dioxide (sc-CO(2)) that avoids the use of organic solvents such as toluene or dioxane are described. The effects of reaction temperature, pressure and time on the surface coverage of the supercritical fluid generated silica hydride intermediate were studied. Under optimised supercritical conditions of 120°C, 483 bar and 3 h reaction time, silica hydride (Si-H) conversion efficiencies of ca. 40% were achieved for the hydride intermediate prepared from a monofunctional silane reagent (dimethylmethoxysilane). Si-H conversion efficiencies (as determined from (29)Si CP-MAS NMR spectral analysis) for the hydride intermediate prepared from triethoxysilane (TES) in sc-CO(2) were found to be comparable to those obtained using a TES silanisation approach in an organic solvent. (13)C and (29)Si CP-MAS-NMR spectroscopy was employed to provide a complete structural assignment of the silica hydride intermediates. Furthermore, supercritical CO(2) was subsequently employed as a reaction medium for the heterogenous hydrosilation of silica hydride with octadecene and with styrene, in the presence of a free radical initiator. These supercritical fluid generated reversed-phase materials were prepared in a substantially reduced reaction time (3 h) compared to organic solvent based methods (100 h reaction time). Silica functionalisation in sc-CO(2) presents an efficient and clean alternative to organic solvent based methods for the preparation of important silica hydride intermediate and silica bonded stationary phases via a hydrosilation approach. Copyright © 2010 Elsevier B.V. All rights reserved.

Hydride heat pump

DOEpatents

Cottingham, James G.

1977-01-01

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

Metal hydride composition and method of making

DOE Office of Scientific and Technical Information (OSTI.GOV)

Congdon, J.W.

1995-08-22

A dimensionally stable hydride composition and a method for making such a composition are disclosed. The composition is made by forming particles of a metal hydride into porous granules, mixing the granules with a matrix material, forming the mixture into pellets, and sintering the pellets in the absence of oxygen. The ratio of matrix material to hydride is preferably between approximately 2:1 and 4:1 by volume. The porous structure of the granules accommodates the expansion that occurs when the metal hydride particles absorb hydrogen. The porous matrix allows the flow of hydrogen there through to contact the hydride particles, yetmore » supports the granules and contains the hydride fines that result from repeated absorption/desorption cycles. 3 figs.« less

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

PubMed

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

2017-05-22

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

Metal Hydride Compression

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, Terry A.; Bowman, Robert; Smith, Barton

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

Liquid suspensions of reversible metal hydrides

DOEpatents

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

1983-12-08

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

Sealed aerospace metal-hydride batteries

NASA Technical Reports Server (NTRS)

Coates, Dwaine

1992-01-01

Nickel metal hydride and silver metal hydride batteries are being developed for aerospace applications. There is a growing market for smaller, lower cost satellites which require higher energy density power sources than aerospace nickel-cadmium at a lower cost than space nickel-hydrogen. These include small LEO satellites, tactical military satellites and satellite constellation programs such as Iridium and Brilliant Pebbles. Small satellites typically do not have the spacecraft volume or the budget required for nickel-hydrogen batteries. NiCd's do not have adequate energy density as well as other problems such as overcharge capability and memory effort. Metal hydride batteries provide the ideal solution for these applications. Metal hydride batteries offer a number of advantages over other aerospace battery systems.

Direct synthesis of catalyzed hydride compounds

DOEpatents

Gross, Karl J.; Majzoub, Eric

2004-09-21

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

Metal hydride compositions and lithium ion batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Young, Kwo; Nei, Jean

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

Determination of total arsenic and arsenic(III) in phosphate fertilizers by hydride generation atomic absorption spectrometry after ultrasound-assisted extraction based on a control acid media.

PubMed

Rezende, Helen Cristine; Coelho, Nivia Maria Melo

2014-01-01

An ultrasound-assisted extraction procedure was developed for determination of inorganic arsenic (As) in phosphate fertilizer by hydride generation atomic absorption spectrometry. The variables that affect the hydride generation step were optimized, including the reducer, acid, sample flow rate, and concentrations of the acid and reducer. The determination of As(lll) was performed through the simple control of solution pH with a 0.5 M citric acid-sodium citrate buffer solution at pH 4.5, and total As was determined after a pre-reduction reaction with 1.0% (w/v) thiourea. Ultrasound-assisted acid extraction was performed, and the parameters sonication time and acid and Triton X-114 concentrations were optimized using a 23 factorial design and central composite design. LODs for As(lll) and total As were 0.029 and 0.022 microg/L, respectively. The accuracy of the method was confirmed with certified reference materials. The method was successfully applied in the determination of inorganic As in phosphate fertilizer samples.

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

DOEpatents

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

1997-01-01

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

Methyl cation affinities of neutral and anionic maingroup-element hydrides: trends across the periodic table and correlation with proton affinities.

PubMed

Mulder, R Joshua; Guerra, Célia Fonseca; Bickelhaupt, F Matthias

2010-07-22

We have computed the methyl cation affinities in the gas phase of archetypal anionic and neutral bases across the periodic table using ZORA-relativistic density functional theory (DFT) at BP86/QZ4P//BP86/TZ2P. The main purpose of this work is to provide the methyl cation affinities (and corresponding entropies) at 298 K of all anionic (XH(n-1)(-)) and neutral bases (XH(n)) constituted by maingroup-element hydrides of groups 14-17 and the noble gases (i.e., group 18) along the periods 2-6. The cation affinity of the bases decreases from H(+) to CH(3)(+). To understand this trend, we have carried out quantitative bond energy decomposition analyses (EDA). Quantitative correlations are established between the MCA and PA values.

Metastable Metal Hydrides for Hydrogen Storage

DOE PAGES

Graetz, Jason

2012-01-01

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

Program Helps Generate Boundary-Element Mathematical Models

NASA Technical Reports Server (NTRS)

Goldberg, R. K.

1995-01-01

Composite Model Generation-Boundary Element Method (COM-GEN-BEM) computer program significantly reduces time and effort needed to construct boundary-element mathematical models of continuous-fiber composite materials at micro-mechanical (constituent) scale. Generates boundary-element models compatible with BEST-CMS boundary-element code for anlaysis of micromechanics of composite material. Written in PATRAN Command Language (PCL).

Arsenic Speciation of Waters from the Aegean Region, Turkey by Hydride Generation: Atomic Absorption Spectrometry.

PubMed

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.

Tellurium speciation analysis using hydride generation in situ trapping electrothermal atomic absorption spectrometry and ruthenium or palladium modified graphite tubes.

PubMed

Yildirim, Emrah; Akay, Pınar; Arslan, Yasin; Bakirdere, Sezgin; Ataman, O Yavuz

2012-12-15

Speciation of tellurium can be achieved by making use of different kinetic behaviors of Te(IV) and Te(VI) upon their reaction with sodium borohydride using hydride generation. While Te(IV) can form H(2)Te, Te(VI) will not form any volatile species during the course of hydride formation and measurement by atomic absorption spectrometry. Quantitative reduction of Te(VI) was achieved through application of a microwave assisted prereduction of Te(VI) in 6.0 mol/L HCl solution. Enhanced sensitivity was achieved by in situ trapping of the generated H(2)Te species in a previously heated graphite furnace whose surface was modified using Pd or Ru. Overall efficiency for in situ trapping in pyrolytically coated graphite tube surface was found to be 15% when volatile analyte species are trapped for 60s at 300°C. LOD and LOQ values were calculated as 0.086 ng/mL and 0.29 ng/mL, respectively. Efficiency was increased to 46% and 36% when Pd and Ru surface modifiers were used, respectively. With Ru modified graphite tube 173-fold enhancement was obtained over 180 s trapping period with respect to ETAAS; the tubes could be used for 250 cycles. LOD values were 0.0064 and 0.0022 ng/mL for Pd and Ru treated ETAAS systems, respectively, for 180 s collection of 9.6 mL sample solution. Copyright © 2012 Elsevier B.V. All rights reserved.

Iron hydrides formation in interstellar clouds

NASA Astrophysics Data System (ADS)

Bar-Nun, A.; Pasternak, M.; Barrett, P. H.

1980-07-01

A recent Moessbauer study with Fe-57 in a solid hydrogen or hydrogen-argon matrix demonstrated the formation of an iron hydride molecule (FeH2) at 2.5-5 K. Following this and other studies, the possible existence of iron hydride molecules in interstellar clouds is proposed. In clouds, the iron hydrides FeH and FeH2 would be formed only on grains, by encounters of H atoms or H2 molecules with Fe atoms which are adsorbed on the grains. The other transition metals, Sc, Ti, V, Cr, Mn, Co, N, Cd and also Cu and Ca form hydrides of the type M-H, which could be responsible, at least in part, for the depletion of these metals in clouds.

Advanced nickel-metal hydride cell development at Hughes: A joint work with US government

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lim, H.S.; Pickett, D.F.; Stockel, J.F.

1995-07-01

Hughes is currently engaged in the development of an advanced nickel-metal hydride (Ni/MHx) cell for spacecraft application with performance goals of 15 years of operation in a geosynchronous earth orbit at 805 depth of discharge and over 30,000 cycles of life at 30% depth of discharge in a typical low earth orbit. The authors have developed the basic fabrication technique for a lightweight and potentially long life nickel electrode which is usable in space Ni/MHx cells. The authors have developed several attractive hydride alloys which are usable in hydride electrodes and basic fabrication techniques for lightweight, inexpensive, and potentially longmore » life hydride electrodes for a Ni/MHx cell. Utilizing Hughes extensive experiences in development of advanced Ni/Cd and Ni/H{sub 2} cells, the authors plan to develop a first generation space Ni/MHx cell design by 1995 and have the cell flight ready by 1997.« less

Mechanistic insights into iron catalyzed dehydrogenation of formic acid: β-hydride elimination vs. direct hydride transfer.

PubMed

Yang, Xinzheng

2013-09-07

Density functional theory calculations reveal a complete reaction mechanism with detailed energy profiles and transition state structures for the dehydrogenation of formic acid catalyzed by an iron complex, [P(CH2CH2PPh2)3FeH](+). In the cationic reaction pathway, a β-hydride elimination process is confirmed to be the rate-determining step in this catalytic reaction. A potential reaction pathway starting with a direct hydride transfer from HCOO(-) to Fe is found to be possible, but slightly less favorable than the catalytic cycle with a β-hydride elimination step.

A classical but new kinetic equation for hydride transfer reactions.

PubMed

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

2013-09-28

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

Inhibited solid propellant composition containing beryllium hydride

NASA Technical Reports Server (NTRS)

Thompson, W. W. (Inventor)

1978-01-01

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

49 CFR 173.311 - Metal hydride storage systems.

Code of Federal Regulations, 2013 CFR

2013-10-01

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

49 CFR 173.311 - Metal hydride storage systems.

Code of Federal Regulations, 2011 CFR

2011-10-01

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

49 CFR 173.311 - Metal hydride storage systems.

Code of Federal Regulations, 2014 CFR

2014-10-01

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

Determination of arsenic in ambient water at sub-part-per-trillion levels by hydride generation Pd coated platform collection and GFAAS detection.

PubMed

Liang, L; Lazoff, S; Chan, C; Horvat, M; Woods, J S

1998-11-01

A method for trace determination of total arsenic in ambient waters is described. Arsenic is separated on-line from a large volume water sample by hydride generation and purging, pre-collected on a Pd coated pyrolytic platform cuvette using a simple and inexpensive system, and finally detected by GFAAS. Instrument parameters, hydride generation, transportation, and collection were optimized. The analytical behavior for major species including As(3+), As(5+), monomethyl As (MMA), and dimethyl As (DMA) were investigated individually. Problems arising from use of the system were discussed and eliminated. The necessity of sample digestion and an efficient digestion method were studied. Sample digestion for water with low organic content such as tap water and clean ground water and some clean surface water can be omitted. The method detection limit (MDL) is 0.3 ng l(-1) for a 25 ml water sample. Recoveries close to 100% with R.S.D.<5% can be easily achieved. Typical aqueous samples including tap, ground, lake, river, rain, sewage effluent, and saline water from different origins in the US, China, and Canada were collected and analyzed using ultra clean sampling and analysis techniques. The background levels of As in most water analyzed were established for the first time, and found to be far above the EPA's health effect criteria, 18 ng l(-1).

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

NASA Astrophysics Data System (ADS)

Voskuilen, Tyler G.

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

Electrochemical process and production of novel complex hydrides

DOEpatents

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.

Structural Characterization of Metal Hydrides for Energy Applications

NASA Astrophysics Data System (ADS)

George, Lyci

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

METHOD AND APPARATUS FOR MAKING URANIUM-HYDRIDE COMPACTS

DOEpatents

Wellborn, W.; Armstrong, J.R.

1959-03-10

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

SYSTEM OPTIMIZATION FOR THE AUTOMATIC SIMULTANEOUS DETERMINATION OF ARSENIC, SELENIUM, AND ANTIMONY, USING HYDRIDE GENERATION INTRODUCTION TO AN INDUCTIVELY COUPLED PLASMA.

USGS Publications Warehouse

Pyen, Grace S.; Browner, Richard F.; Long, Stephen

1986-01-01

A fixed-size simplex has been used to determine the optimum conditions for the simultaneous determination of arsenic, selenium, and antimony by hydride generation and inductively coupled plasma emission spectrometry. The variables selected for the simplex were carrier gas flow rate, rf power, viewing height, and reagent conditions. The detection limit for selenium was comparable to the preoptimized case, but there were twofold and fourfold improvements in the detection limits for arsenic and antimony, respectively. Precision of the technique was assessed with the use of artificially prepared water samples.

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

NASA Technical Reports Server (NTRS)

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.

Use of reversible hydrides for hydrogen storage

NASA Technical Reports Server (NTRS)

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

1980-01-01

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

Results of NDE Technique Evaluation of Clad Hydrides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kunerth, Dennis C.

2014-09-01

This report fulfills the M4 milestone, M4FT-14IN0805023, Results of NDE Technique Evaluation of Clad Hydrides, under Work Package Number FT-14IN080502. During service, zirconium alloy fuel cladding will degrade via corrosion/oxidation. Hydrogen, a byproduct of the oxidation process, will be absorbed into the cladding and eventually form hydrides due to low hydrogen solubility limits. The hydride phase is detrimental to the mechanical properties of the cladding and therefore it is important to be able to detect and characterize the presence of this constituent within the cladding. Presently, hydrides are evaluated using destructive examination. If nondestructive evaluation techniques can be used tomore » 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

Hydride affinity scale of various substituted arylcarbeniums in acetonitrile.

PubMed

Zhu, Xiao-Qing; Wang, Chun-Hua

2010-12-23

Combined with the integral equation formalism polarized continuum model (IEFPCM), the hydride affinities of 96 various acylcarbenium ions in the gas phase and CH(3)CN were estimated by using the B3LYP/6-31+G(d)//B3LYP/6-31+G(d), B3LYP/6-311++G(2df,2p)//B3LYP/6-31+G(d), and BLYP/6-311++G(2df,2p)//B3LYP/6-31+G(d) methods for the first time. The results show that the combination of the BLYP/6-311++G(2df,2p)//B3LYP/6-31+G(d) method and IEFPCM could successfully predict the hydride affinities of arylcarbeniums in MeCN with a precision of about 3 kcal/mol. On the basis of the calculated results from the BLYP method, it can be found that the hydride affinity scale of the 96 arylcarbeniums in MeCN ranges from -130.76 kcal/mol for NO(2)-PhCH(+)-CN to -63.02 kcal/mol for p-(Me)(2)N-PhCH(+)-N(Me)(2), suggesting most of the arylcarbeniums are good hydride acceptors. Examination of the effect of the number of phenyl rings attached to the carbeniums on the hydride affinities shows that the increase of the hydride affinities takes place linearly with increasing number of benzene rings in the arylcarbeniums. Analyzing the effect of the substituents on the hydride affinities of arylcarbeniums indicates that electron-donating groups decrease the hydride affinities and electron-withdrawing groups show the opposite effect. The hydride affinities of arylcarbeniums are linearly dependent on the sum of the Hammett substituent parameters σ(p)(+). Inspection of the correlation of the solution-phase hydride affinities with gas-phase hydride affinities and aqueous-phase pK(R)(+) values reveals a remarkably good correspondence of ΔG(H(-)A)(R(+)) with both the gas-phase relative hydride affinities only if the α substituents X have no large electron-donating or -withdrawing properties and the pK(R)(+) values even though the media are dramatically different. The solution-phase hydride affinities also have a linear relationship with the electrophilicity parameter E, and this dependence can

Model for the Prediction of the Hydriding Thermodynamics of Pd-Rh-Co Ternary Alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Teter, D.F.; Thoma, D.J.

1999-03-01

A dilute solution model (with respect to the substitutional alloying elements) has been developed, which accurately predicts the hydride formation and decomposition thermodynamics and the storage capacities of dilute ternary Pd-Rh-Co alloys. The effect of varying the rhodium and cobalt compositions on the thermodynamics of hydride formation and decomposition and hydrogen capacity of several palladium-rhodium-cobalt ternary alloys has been investigated using pressure-composition (PC) isotherms. Alloying in the dilute regime (<10 at.%) causes the enthalpy for hydride formation to linearly decrease with increasing alloying content. Cobalt has a stronger effect on the reduction in enthalpy than rhodium for equivalent alloying amounts.more » Also, cobalt reduces the hydrogen storage capacity with increasing alloying content. The plateau thermodynamics are strongly linked to the lattice parameters of the alloys. A near-linear dependence of the enthalpy of hydride formation on the lattice parameter was observed for both the binary Pd-Rh and Pd-Co alloys, as well as for the ternary Pd-Rh-Co alloys. The Pd-5Rh-3Co (at. %) alloy was found to have similar plateau thermodynamics as a Pd-10Rh alloy, however, this ternary alloy had a diminished hydrogen storage capacity relative to Pd-10Rh.« less

Nanoindentation study of bulk zirconium hydrides at elevated temperatures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cinbiz, Mahmut Nedim; Balooch, Mehdi; Hu, Xunxiang

Here, the mechanical properties of zirconium hydrides was studied using nano-indentation technique at a temperature range of 25 – 400 °C. Temperature dependency of reduced elastic modulus and hardness of δ- and ε-zirconium hydrides were obtained by conducting nanoindentation experiments on the bulk hydride samples with independently heating capability of indenter and heating stage. The reduced elastic modulus of δ-zirconium hydride (H/Zr ratio =1.61) decreased from ~113 GPa to ~109 GPa while temperature increased from room temperature to 400°C. For ε-zirconium hydrides (H/Zr ratio=1.79), the reduced elastic modulus decreased from 61 GPa to 54 GPa as temperature increased from roommore » temperature to 300 °C. Whereas, hardness of δ-zirconium hydride significantly decreased from 4.1 GPa to 2.41 GPa when temperature increased from room temperature to 400 °C. Similarly, hardness of ε-zirconium hydride decreased from 3.06 GPa to 2.19 GPa with temperature increase from room temperature to 300°C.« less

Nanoindentation study of bulk zirconium hydrides at elevated temperatures

DOE PAGES

Cinbiz, Mahmut Nedim; Balooch, Mehdi; Hu, Xunxiang; ...

2017-08-02

Here, the mechanical properties of zirconium hydrides was studied using nano-indentation technique at a temperature range of 25 – 400 °C. Temperature dependency of reduced elastic modulus and hardness of δ- and ε-zirconium hydrides were obtained by conducting nanoindentation experiments on the bulk hydride samples with independently heating capability of indenter and heating stage. The reduced elastic modulus of δ-zirconium hydride (H/Zr ratio =1.61) decreased from ~113 GPa to ~109 GPa while temperature increased from room temperature to 400°C. For ε-zirconium hydrides (H/Zr ratio=1.79), the reduced elastic modulus decreased from 61 GPa to 54 GPa as temperature increased from roommore » temperature to 300 °C. Whereas, hardness of δ-zirconium hydride significantly decreased from 4.1 GPa to 2.41 GPa when temperature increased from room temperature to 400 °C. Similarly, hardness of ε-zirconium hydride decreased from 3.06 GPa to 2.19 GPa with temperature increase from room temperature to 300°C.« less

G2(+)M study on N-alkylamino cation affinities of neutral main-group element hydrides: trends across the periodic table.

PubMed

Geng, Song; Wu, Ding-Lu; Yang, Jing; Wei, Xi-Guang; Zhu, Jun; Zhang, Hai-Bo; Ren, Yi; Lau, Kai-Chung

2014-05-08

We have made an extensive theoretical exploration of gas-phase N-alkylamino cation affinities (NAAMCA), including amino cation affinities (AMCA) and N-dimethylamino cation affinities (NDMAMCA), of neutral main-group element hydrides of groups 15-17 and periods 2-4 in the periodic table by using the G2(+)M method. Some similarities and differences are found between NAAMCA and the corresponding alkyl cation affinities (ACA) of H(n)X. Our calculations show that the AMCA and NDMAMCA are systematically lower than the corresponding proton affinities (PA) for H(n)X. In general, there is no linear correlation between NAAMCA and PA of H(n)X. Instead, the correlations exist only within the central elements X in period 2, or periods 3-4, which is significantly different from the reasonable correlations between ACA and PA for all H(n)X. NAAMCA (H(n)X) are weaker than NAAMCA (H(n-1)X(-)) by more than 700 kJ/mol and generally stronger than ACA (H(n)X), with three exceptions: H2ONR2(+)(R = H, Me) and HFNH2(+). These new findings can be rationalized by the negative hyperconjugation and Pauli repulsion.

Chemical Hydride Slurry for Hydrogen Production and Storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

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% MgH 2 slurry was demonstrated, which was just short of the 76% goal. This slurry is pumpable and storable for months at amore » 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 University

Oxidation State Specific Generation of Arsines from Methylated Arsenicals Based on L- Cysteine Treatment in Buffered Media for Speciation Analysis by Hydride Generation - Automated Cryotrapping - Gas Chromatography-Atomic Absorption Spectrometry with the Multiatomizer

PubMed Central

Matoušek, Tomáš; Hernández-Zavala, Araceli; Svoboda, Milan; Langrová, Lenka; Adair, Blakely M.; Drobná, Zuzana; Thomas, David J.; Stýblo, Miroslav; Dědina, Jiří

2008-01-01

An automated system for hydride generation - cryotrapping- gas chromatography - atomic absorption spectrometry with the multiatomizer is described. Arsines are preconcentrated and separated in a Chromosorb filled U-tube. An automated cryotrapping unit, employing nitrogen gas formed upon heating in the detection phase for the displacement of the cooling liquid nitrogen, has been developed. The conditions for separation of arsines in a Chromosorb filled U-tube have been optimized. A complete separation of signals from arsine, methylarsine, dimethylarsine, and trimethylarsine has been achieved within a 60 s reading window. The limits of detection for methylated arsenicals tested were 4 ng l−1. Selective hydride generation is applied for the oxidation state specific speciation analysis of inorganic and methylated arsenicals. The arsines are generated either exclusively from trivalent or from both tri- and pentavalent inorganic and methylated arsenicals depending on the presence of L-cysteine as a prereductant and/or reaction modifier. A TRIS buffer reaction medium is proposed to overcome narrow optimum concentration range observed for the L-cysteine modified reaction in HCl medium. The system provides uniform peak area sensitivity for all As species. Consequently, the calibration with a single form of As is possible. This method permits a high-throughput speciation analysis of metabolites of inorganic arsenic in relatively complex biological matrices such as cell culture systems without sample pretreatment, thus preserving the distribution of tri- and pentavalent species. PMID:18521190

Hydride heat pump with heat regenerator

NASA Technical Reports Server (NTRS)

Jones, Jack A. (Inventor)

1991-01-01

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

Determination of Inorganic Arsenic in a Wide Range of Food Matrices using Hydride Generation - Atomic Absorption Spectrometry.

PubMed

de la Calle, Maria B; Devesa, Vicenta; Fiamegos, Yiannis; Vélez, Dinoraz

2017-09-01

The European Food Safety Authority (EFSA) underlined in its Scientific Opinion on Arsenic in Food that in order to support a sound exposure assessment to inorganic arsenic through diet, information about distribution of arsenic species in various food types must be generated. A method, previously validated in a collaborative trial, has been applied to determine inorganic arsenic in a wide variety of food matrices, covering grains, mushrooms and food of marine origin (31 samples in total). The method is based on detection by flow injection-hydride generation-atomic absorption spectrometry of the iAs selectively extracted into chloroform after digestion of the proteins with concentrated HCl. The method is characterized by a limit of quantification of 10 µg/kg dry weight, which allowed quantification of inorganic arsenic in a large amount of food matrices. Information is provided about performance scores given to results obtained with this method and which were reported by different laboratories in several proficiency tests. The percentage of satisfactory results obtained with the discussed method is higher than that of the results obtained with other analytical approaches.

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

DOEpatents

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

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.

Porous metal hydride composite and preparation and uses thereof

DOEpatents

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

1980-03-12

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

Porous metal hydride composite and preparation and uses thereof

DOEpatents

Steyert, William A.; Olsen, Clayton E.

1982-01-01

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

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

NASA Astrophysics Data System (ADS)

Soo Kim, Yeon; Wang, Wei-E.; Olander, D. R.; Yagnik, S. K.

1997-07-01

Hydriding kinetics of thin sponge-Zr layers metallurgically bonded to a Zircaloy disk has been studied by thermogravimetry in the temperature range 350-400°C in 7 MPa hydrogen-steam mixtures. Some specimens were prefilmed with a thin oxide layer prior to exposure to the reactant gas; all were coated with a thin layer of gold to avoid premature reaction at edges. Two types of hydriding were observed in prefilmed specimens, viz., a slow hydrogen absorption process that precedes an accelerated (massive) hydriding. At 7 MPa total pressure, the critical ratio of H 2/H 2O above which massive hydriding occurs at 400°C is ˜ 200. The critical H 2/H 20 ratio is shifted to ˜2.5 × 103 at 350°C. The slow hydriding process occurs only when conditions for hydriding and oxidation are approximately equally favorable. Based on maximum weight gain, the specimen is completely converted to δ-ZrH 2 by massive hydriding in ˜5 h at a hydriding rate of ˜10 -6 mol H/cm 2 s. Incubation times of 10-20 h prior to the onset of massive hydriding increases with prefilm oxide thickness in the range of 0-10 μm. By changing to a steam-enriched gas, massive hydriding that initially started in a steam-starved condition was arrested by re-formation of a protective oxide scale.

Storing hydrogen in the form of light alloy hydrides

NASA Technical Reports Server (NTRS)

Freund, E.; Gillerm, C.

1981-01-01

Different hydrides are investigated to find a system with a sufficiently high storage density (at least 3%). The formation of hydrides with light alloys is examined. Reaction kinetics for hydride formation were defined and applied to the systems Mg-Al-H, Mg-Al-Cu-H, Ti-Al-H, Ti-Al-Cu-H, and Ti-Al-Ni-H. Results indicate that the addition of Al destabilizes MgH2 and TiH2 hydrides while having only a limited effect on the storage density.

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

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

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

Bipolar Nickel-Metal Hydride Battery Being Developed

NASA Technical Reports Server (NTRS)

Manzo, Michelle A.

1998-01-01

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

Quantifying uncertainty in the measurement of arsenic in suspended particulate matter by Atomic Absorption Spectrometry with hydride generator

PubMed Central

2011-01-01

Arsenic is the toxic element, which creates several problems in human being specially when inhaled through air. So the accurate and precise measurement of arsenic in suspended particulate matter (SPM) is of prime importance as it gives information about the level of toxicity in the environment, and preventive measures could be taken in the effective areas. Quality assurance is equally important in the measurement of arsenic in SPM samples before making any decision. The quality and reliability of the data of such volatile elements depends upon the measurement of uncertainty of each step involved from sampling to analysis. The analytical results quantifying uncertainty gives a measure of the confidence level of the concerned laboratory. So the main objective of this study was to determine arsenic content in SPM samples with uncertainty budget and to find out various potential sources of uncertainty, which affects the results. Keeping these facts, we have selected seven diverse sites of Delhi (National Capital of India) for quantification of arsenic content in SPM samples with uncertainty budget following sampling by HVS to analysis by Atomic Absorption Spectrometer-Hydride Generator (AAS-HG). In the measurement of arsenic in SPM samples so many steps are involved from sampling to final result and we have considered various potential sources of uncertainties. The calculation of uncertainty is based on ISO/IEC17025: 2005 document and EURACHEM guideline. It has been found that the final results mostly depend on the uncertainty in measurement mainly due to repeatability, final volume prepared for analysis, weighing balance and sampling by HVS. After the analysis of data of seven diverse sites of Delhi, it has been concluded that during the period from 31st Jan. 2008 to 7th Feb. 2008 the arsenic concentration varies from 1.44 ± 0.25 to 5.58 ± 0.55 ng/m3 with 95% confidence level (k = 2). PMID:21466671

In situ hydride formation in titanium during focused ion milling.

PubMed

Ding, Rengen; Jones, Ian P

2011-01-01

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

Application of ICP-MS as a multi-element detector for sulfur and metal hydride impurities in hydrocarbon matrices.

PubMed

Geiger, William M; McSheehy, Shona; Nash, Martin J

2007-01-01

Maturation of inductively coupled plasma-mass spectrometry (ICP-MS) in terms of size, reliability, and cost has had a significant impact on its consideration as a viable detector for gas chromatography. Its generally excellent sensitivity for those elements it can measure has been a contributing factor. A method for sulfur speciation in various hydrocarbon products is investigated, as well as sulfur and metal hydride contaminants in high purity hydrocarbon feed stocks. Detection limits for sulfur species in hydrocarbon liquids and gases are approximately 5 and 10 ppb, respectively, as sulfur. Lower detection limits on the order of 100 parts per trillion are achieved for arsine. The use of collision cell technology (CCT) is exploited to remove interferences. CCT has been described elsewhere (1) using helium or helium-hydrogen mixtures for suppression of (16)O(16)O(+) interference with (32)S. In this work, a novel approach is investigated which uses oxygen to remove this interference by shifting it in a comprehensive fashion. The advantage of operating the system at full power with a tandem gas and liquid interface is also discussed.

Low density metal hydride foams

DOEpatents

Maienschein, Jon L.; Barry, Patrick E.

1991-01-01

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

Method of making crack-free zirconium hydride

DOEpatents

Sullivan, Richard W.

1980-01-01

Crack-free hydrides of zirconium and zirconium-uranium alloys are produced by alloying the zirconium or zirconium-uranium alloy with beryllium, or nickel, or beryllium and scandium, or nickel and scandium, or beryllium and nickel, or beryllium, nickel and scandium and thereafter hydriding.

Characterization of laser induced breakdown plasmas used for measurements of arsenic, antimony and selenium hydrides

NASA Astrophysics Data System (ADS)

Simeonsson, J. B.; Williamson, L. J.

2011-09-01

Studies have been performed to characterize laser induced breakdown spectroscopy (LIBS) plasmas formed in Ar/H 2 gas mixtures that are used for hydride generation (HG) LIBS measurements of arsenic (As), antimony (Sb) and selenium (Se) hydrides. The plasma electron density and plasma excitation temperature have been determined through hydrogen, argon and arsenic emission measurements. The electron density ranges from 4.5 × 10 17 to 8.3 × 10 15 cm -3 over time delays of 0.2 to 15 μs. The plasma temperatures range from 8800 to 7700 K for Ar and from 8800 to 6500 K for As in the HG LIBS plasmas. Evaluation of the plasma properties leads to the conclusion that partial local thermodynamic equilibrium conditions are present in the HG LIBS plasmas. Comparison measurements in LIBS plasmas formed in Ar gas only indicate that the temperatures are similar in both plasmas. However it is also observed that the electron density is higher in the Ar only plasmas and that the emission intensities of Ar are higher and decay more slowly in the Ar only plasmas. These differences are attributed to the presence of H 2 which has a higher thermal conductivity and provides additional dissociation, excitation and ionization processes in the HG LIBS plasma environment. Based on the observed results, it is anticipated that changes to the HG conditions that change the amount of H 2 in the plasma will have a significant effect on analyte emission in the HG LIBS plasmas that is independent of changes in the HG efficiency. The HG LIBS plasmas have been evaluated for measurements of elements hydrides using a constant set of HG LIBS plasma conditions. Linear responses are observed and limits of detection of 0.7, 0.2 and 0.6 mg/L are reported for As, Sb and Se, respectively.

Flow injection-hydride generation atomic absorption spectrometric determination of selenium, arsenic and bismuth.

PubMed

Zhang, Yanlin; Adeloju, Samuel B

2008-08-15

A simple and robust flow injection system which permits low sample and reagent consumption is described for rapid and reliable hydride generation atomic absorption spectrometric determination of selenium, arsenic and bismuth. The system, which composed of one peristaltic pump and one four channel solenoid valve, used water as the carrier streams for both sample and NaBH(4) solution. Rapid off-line pre-reduction of the analytes was achieved by using hydroxylamine hydrochloride for selenium and a mixture of potassium iodide and ascorbic acid for arsenic and bismuth. Transition metal interference was eliminated with the addition of thiourea and EDTA into the NaBH(4) solution and significant sensitivity enhancement was observed for selenium in the presence of thiourea in the reductant solution. Under optimised conditions, the method achieved detection limits of 0.2 ng mL(-1) for Se, 0.5 ng mL(-1) for As and 0.3 ng mL(-1) for Bi. The method was very reproducible, achieving relative standard deviations of 6.3% for Se, 3.6% for As and 4.7% for Bi, and has a sample throughput of 360 h(-1). Successful application of the method to the quantification of selenium, arsenic and bismuth in a certified reference river sediment sample is reported.

High H⁻ ionic conductivity in barium hydride.

PubMed

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

2015-01-01

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

Reactivity of yttrium carboxylates toward alkylaluminum hydrides.

PubMed

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

2013-11-25

Yttrocene-carboxylate complex [Cp*2Y(OOCAr(Me))] (Cp*=C5Me5, Ar(Me) =C6H2Me3-2,4,6) was synthesized as a spectroscopically versatile model system for investigating the reactivity of alkylaluminum hydrides towards rare-earth-metal carboxylates. Equimolar reactions with bis-neosilylaluminum hydride and dimethylaluminum hydride gave adduct complexes of the general formula [Cp*2Y(μ-OOCAr(Me))(μ-H)AlR2] (R=CH2SiMe3, Me). The use of an excess of the respective aluminum hydride led to the formation of product mixtures, from which the yttrium-aluminum-hydride complex [{Cp*2Y(μ-H)AlMe2(μ-H)AlMe2(μ-CH3)}2] could be isolated, which features a 12-membered-ring structure. The adduct complexes [Cp*2Y(μ-OOCAr(Me))(μ-H)AlR2] display identical (1)J(Y,H) coupling constants of 24.5 Hz for the bridging hydrido ligands and similar (89)Y NMR shifts of δ=-88.1 ppm (R=CH2SiMe3) and δ=-86.3 ppm (R=Me) in the (89)Y DEPT45 NMR experiments. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultra-Shallow Depth Profiling of Arsenic Implants in Silicon by Hydride Generation-Inductively Coupled Plasma Atomic Emission Spectrometry

NASA Astrophysics Data System (ADS)

Matsubara, Atsuko; Kojima, Hisao; Itoga, Toshihiko; Kanehori, Keiichi

1995-08-01

High resolution depth profiling of arsenic (As) implanted into silicon wafers by a chemical technique is described. Silicon wafers are precisely etched through repeated oxidation by hydrogen peroxide solution and dissolution of the oxide by hydrofluoric acid solution. The etched silicon thickness is determined by inductively-coupled plasma atomic emission spectrometry (ICP-AES). Arsenic concentration is determined by hydride generation ICP-AES (HG-ICP-AES) with prereduction using potassium iodide. The detection limit of As in a 4-inch silicon wafer is 2.4×1018 atoms/cm3. The etched silicon thickness is controlled to less than 4±2 atomic layers. Depth profiling of an ultra-shallow As diffusion layer with the proposed method shows good agreement with profiling using the four-probe method or secondary ion mass spectrometry.

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

PubMed Central

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

Liquid chromatography-hydride generation-atomic absorption spectrometry for the speciation of tin in seafoods.

PubMed

Viñas, Pilar; López-García, Ignacio; Merino-Meroño, Beatriz; Campillo, Natalia; Hernández-Cordóba, Manuel

2004-04-01

Liquid chromatography with hydride generation atomic absorption spectrometry as the detection system was applied to the separation and determination of inorganic tin, tributyltin, dibutyltin, monobutyltin, diphenyltin and monophenyltin. A reversed phase C18 column and a methanol/water/acetic acid (70:27:3, v/v/v) mixture containing 0.05%(v/v) triethylamine and 0.1%(w/v) tropolone as the mobile phase (isocratic elution) were used. Extraction of organotins from the samples was carried out using methanol containing 0.05%(w/v) tropolone, a process that was repeated twice. The supernatants were shaken with water and dichloromethane in a separating funnel and the organic phase was collected and evaporated to dryness. When the method was applied to the speciation of tin in fresh and canned mussels, no organotins above the detection limits were identified in any of the samples, inorganic tin being the only species detected. The reliability of the procedure was checked by analyzing the total tin content of the samples by electrothermal atomic absorption spectrometry and by speciation of tin in a certified reference material, mussel tissue (CRM 477). The method can be used for environmental monitoring of organotins contaminated samples.

Organotin speciation in environmental matrices by automated on-line hydride generation-programmed temperature vaporization-capillary gas chromatography-mass spectrometry detection.

PubMed

Serra, H; Nogueira, J M F

2005-11-11

In the present contribution, a new automated on-line hydride generation methodology was developed for dibutyltin and tributyltin speciation at the trace level, using a programmable temperature-vaporizing inlet followed by capillary gas chromatography coupled to mass spectrometry in the selected ion-monitoring mode acquisition (PTV-GC/MS(SIM)). The methodology involves a sequence defined by two running methods, the first one configured for hydride generation with sodium tetrahydroborate as derivatising agent and the second configured for speciation purposes, using a conventional autosampler and data acquisition controlled by the instrument's software. From the method-development experiments, it had been established that injector configuration has a great effect on the speciation of the actual methodology, particularly, the initial inlet temperature (-20 degrees C; He: 150 ml/min), injection volume (2 microl) and solvent characteristics using the solvent venting mode. Under optimized conditions, a remarkable instrumental performance including very good precision (RSD < 4%), excellent linear dynamic range (up to 50 microg/ml) and limits of detection of 0.12 microg/ml and 9 ng/ml, were obtained for dibutyltin and tributyltin, respectively. The feasibility of the present methodology was validated through assays upon in-house spiked water (2 ng/ml) and a certified reference sediment matrix (Community Bureau of Reference, CRM 462, Nr. 330 dibutyltin: 68+/-12 ng/g; tributyltin: 54+/-15 ng/g on dry mass basis), using liquid-liquid extraction (LLE) and solid-phase extraction (SPE) sample enrichment and multiple injections (2 x 5 microl) for sensitivity enhancement. The methodology evidenced high reproducibility, is easy to work-up, sensitive and showed to be a suitable alternative to replace the currently dedicated analytical systems for organotin speciation in environmental matrices at the trace level.

SPECIATION OF SELENIUM AND ARSENIC COMPOUNDS BY CAPILLARY ELECTROPHORESIS WITH HYDRODYNAMICALLY MODIFIED ELECTROOSMOTIC FLOW AND ON-LINE REDUCTION OF SELENIUM(VI) TO SELENIUM(IV) WITH HYDRIDE GENERATION INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRIC DETECTION

EPA Science Inventory

Capillary electrophoresis (CE) with hydride generation inductively coupled plasma mass spectrometry was used to determine four arsenicals and two selenium species. Selenate (SeVI) was reduced on-line to selenite (SeIV') by mixing the CE effluent with concentrated HCl. A microporo...

Heterogeneous reduction of carbon dioxide by hydride-terminated silicon nanocrystals

PubMed Central

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

Advanced nickel-metal hydride cell development at Hughes: A joint work with US government

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lim, H.S.; Pickett, D.F.; Stockel, J.F.

1995-01-25

Hughes is currently engaged in the development of an advanced nickel-metal hydride (Ni/MHx) cell for spacecraft application with performance goals of 15 years of opertion in a geosynchronous earth orbit at 80% depth of discharge and over 30,000 cycles of life at 30% depth of discharge in a typical low earth orbit. We have developed the basic fabrication technique for a lightweight and potentially long life nickel electrode which is useable in space Ni/MHx cells. We have developed several attractive hydride alloys which are useable in hydride electrodes and basic fabrication techniques for lightweight, inexpensive, and potentially long life hydridemore » electrodes for a Ni/MHx cell. Utilizing Hughes extensive experiences in development of advanced Ni/Cd and Ni/H{sub 2} cells, we plan to develop a first generation space Ni/MHx cell design by 1995 and have the cell flight ready by 1997.« less

Laboratory Rotational Spectroscopy of Astrophysical Interesting Diatomic Hydrides

NASA Astrophysics Data System (ADS)

Halfen, DeWayne; Ziurys, L.

2008-05-01

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 entirely in the submillimeter and far-infrared regions. Hence, the future airborne and space-borne platforms, such as SOFIA and Herschel, are primed to explore these prevalent molecules. However, in order to detect these species in the ISM, their rotational spectra must first be measured in the laboratory. Using submillimeter direct absorption methods in the Ziurys laboratory, we have recorded the spectra of several diatomic hydrides of astrophysical interest. We have measured the pure rotational spectrum of MnH (X7Σ+: N = 0 - 1) and MnD (N = 2 - 3), as well as the deuterium and carbon-13 isotopologues of CH, CD (X2Πr: N = 1 - 1 and 1 - 2) and 13CH (N = 1 - 1). Manganese hydride and deuteride were created in a DC discharge of H2 or D2 and manganese vapor, generated in a Broida-type oven. CD and 13CH were produced in an AC discharge of argon and CD4 or 13CH4. For MnH, the five strongest manganese hyperfine transitions were recorded in its N = 0 - 1 transition, each of which are additionally split by hydrogen hyperfine interactions. CD and 13CH also have multiple hyperfine components due to the D, 13C, and/or H atoms. The direct measurement of these fundamental transitions will allow for unambiguous astronomical detections. The results of these studies will be presented.

Development of a component design tool for metal hydride heat pumps

NASA Astrophysics Data System (ADS)

Waters, Essene L.

Given current demands for more efficient and environmentally friendly energy sources, hydrogen based energy systems are an increasingly popular field of interest. Within the field, metal hydrides have become a prominent focus of research due to their large hydrogen storage capacity and relative system simplicity and safety. Metal hydride heat pumps constitute one such application, in which heat and hydrogen are transferred to and from metal hydrides. While a significant amount of work has been done to study such systems, the scope of materials selection has been quite limited. Typical studies compare only a few metal hydride materials and provide limited justification for the choice of those few. In this work, a metal hydride component design tool has been developed to enable the targeted down-selection of an extensive database of metal hydrides to identify the most promising materials for use in metal hydride thermal systems. The material database contains over 300 metal hydrides with various physical and thermodynamic properties included for each material. Sub-models for equilibrium pressure, thermophysical data, and default properties are used to predict the behavior of each material within the given system. For a given thermal system, this tool can be used to identify optimal materials out of over 100,000 possible hydride combinations. The selection tool described herein has been applied to a stationary combined heat and power system containing a high-temperature proton exchange membrane (PEM) fuel cell, a hot water tank, and two metal hydride beds used as a heat pump. A variety of factors can be used to select materials including efficiency, maximum and minimum system pressures, pressure difference, coefficient of performance (COP), and COP sensitivity. The targeted down-selection of metal hydrides for this system focuses on the system's COP for each potential pair. The values of COP and COP sensitivity have been used to identify pairs of highest interest for

Advanced Metal-Hydrides-Based Thermal Battery: A New Generation of High Density Thermal Battery Based on Advanced Metal Hydrides

DOE Office of Scientific and Technical Information (OSTI.GOV)

None

HEATS Project: The University of Utah is developing a compact hot-and-cold thermal battery using advanced metal hydrides that could offer efficient climate control system for EVs. The team’s innovative designs of heating and cooling systems for EVs with high energy density, low-cost thermal batteries could significantly reduce the weight and eliminate the space constraint in automobiles. The thermal battery can be charged by plugging it into an electrical outlet while charging the electric battery and it produces heat and cold through a heat exchanger when discharging. The ultimate goal of the project is a climate-controlling thermal battery that can lastmore » up to 5,000 charge and discharge cycles while substantially increasing the driving range of EVs, thus reducing the drain on electric batteries.« less

Proton affinities of maingroup-element hydrides and noble gases: trends across the periodic table, structural effects, and DFT validation.

PubMed

Swart, Marcel; Rösler, Ernst; Bickelhaupt, F Matthias

2006-10-01

We have carried out an extensive exploration of the gas-phase basicity of archetypal neutral bases across the periodic system using the generalized gradient approximation (GGA) of the density functional theory (DFT) at BP86/QZ4P//BP86/TZ2P. First, we validate DFT as a reliable tool for computing proton affinities and related thermochemical quantities: BP86/QZ4P//BP86/TZ2P is shown to yield a mean absolute deviation of 2.0 kcal/mol for the proton affinity at 298 K with respect to experiment, and 1.2 kcal/mol with high-level ab initio benchmark data. The main purpose of this work is to provide the proton affinities (and corresponding entropies) at 298 K of the neutral bases constituted by all maingroup-element hydrides of groups 15-17 and the noble gases, that is, group 18, and periods 1-6. We have also studied the effect of step-wise methylation of the protophilic center of the second- and third-period bases. Copyright 2006 Wiley Periodicals, Inc.

Improvement of electrochemical properties and oxidation/reduction behavior of cobalt in positive electrode of Ni-metal hydride battery

NASA Astrophysics Data System (ADS)

Morimoto, Katsuya; Nagashima, Ikuo; Matsui, Masaki; Maki, Hideshi; Mizuhata, Minoru

2018-06-01

The deterioration mechanisms of a Ni-metal hydride (Ni-MH) battery system during operation is investigated. A decrease of the discharge voltage is observed at the early stage of the cycle, which indicates the possible occurrence of an unexpected system shutdown of the battery at low state of charge. Cyclic voltammetry and surface examination are used to investigate the causes of this phenomenon. The elution of elements such as Al and Mn from the metal hydride negative electrodes is shown to affect the oxidation/reduction behavior of Co, the conductive material of the positive electrode. Furthermore, the possible methods to strengthen the conductive network of Co, including pretreatment of the positive electrode, addition of conductive material, and precipitation of the elution elements as insoluble compounds to reduce their effect are also investigated. By combining these strategies, deterioration of the conductive network can be prevented in the early stage.

The free-energy barrier to hydride transfer across a dipalladium complex

DOE PAGES

Ramirez-Cuesta, Anibal J.

2015-01-01

We use density-functional theory molecular dynamics (DFT-MD) simulations to determine the hydride transfer coordinate between palladium centres of the crystallographically observed terminal hydride locations, Pd-Pd-H, originally postulated for the solution dynamics of the complex bis-NHC dipalladium hydride [{(MesIm)(2)CH2}(2)Pd2H][PF6], and then calculate the free-energy along this coordinate. We estimate the transfer barrier-height to be about 20 kcal mol(-1) with a hydride transfer rate in the order of seconds at room temperature. We validate our DFT-MD modelling using inelastic neutron scattering which reveals anharmonicity of the hydride environment that is so pronounced that there is complete failure of the harmonic model formore » the hydride ligand. The simulations are extended to high temperature to bring the H-transfer to a rate that is accessible to the simulation technique.« less

Destabilisation of complex hydrides through size effects.

PubMed

Christian, Meganne; Aguey-Zinsou, Kondo-Francois

2010-12-01

Nanoparticles of NaAlH4, LiAlH4 and LiBH4 were prepared by encapsulating their respective hydrides within carbon nanotubes by a wet chemical approach. The resulting confinement had a profound effect on the overall hydrogen storage properties of these hydrides, with NaAlH4 and LiAlH4 releasing hydrogen from room temperature, for example.

AIR PASSIVATION OF METAL HYDRIDE BEDS FOR WASTE DISPOSAL

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klein, J; R. H. Hsu, R

2007-07-02

Metal hydride beds offer compact, safe storage of tritium. After metal hydride beds have reached the end of their useful life, the beds will replaced with new beds and the old beds prepared for disposal. One acceptance criteria for hydride bed waste disposal is that the material inside the bed not be pyrophoric. To determine the pyrophoric nature of spent metal hydride beds, controlled air ingress tests were performed. A simple gas handling manifold fitted with pressure transducers and a calibrated volume were used to introduce controlled quantities of air into a metal hydride bed and the bed temperature risemore » monitored for reactivity with the air. A desorbed, 4.4 kg titanium prototype hydride storage vessel (HSV) produced a 4.4 C internal temperature rise upon the first air exposure cycle and a 0.1 C temperature rise upon a second air exposure. A total of 346 scc air was consumed by the bed (0.08 scc per gram Ti). A desorbed, 9.66 kg LaNi{sub 4.25}Al{sub 0.75} prototype storage bed experienced larger temperature rises over successive cycles of air ingress and evacuation. The cycles were performed over a period of days with the bed effectively passivated after the 12th cycle. Nine to ten STP-L of air reacted with the bed producing both oxidized metal and water.« less

High energy density battery based on complex hydrides

DOEpatents

Zidan, Ragaiy

2016-04-26

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

Application of multivariate techniques in the optimization of a procedure for the determination of bioavailable concentrations of Se and As in estuarine sediments by ICP OES using a concomitant metals analyzer as a hydride generator.

PubMed

Lopes, Watson da Luz; Santelli, Ricardo Erthal; Oliveira, Eliane Padua; de Carvalho, Maria de Fátima Batista; Bezerra, Marcos Almeida

2009-10-15

A procedure has been developed for the determination of bioavailable concentrations of selenium and arsenic in estuarine sediments employing inductively coupled plasma optical emission spectrometry (ICP OES) using a concomitant metals analyzer device to perform hydride generation. The optimization of hydride generation was done in two steps: using a two-level factorial design for preliminary evaluation of studied factors and a Doehlert design to assess the optimal experimental conditions for analysis. Interferences of transition metallic ions (Cd(2+), Co(2+), Cu(2+), Fe(3+) and Ni(2+)) to selenium and arsenic signals were minimized by using higher hydrochloric acid concentrations. In this way, the procedure allowed the determination of selenium and arsenic in sediments with a detection limit of 25 and 30 microg kg(-1), respectively, assuming a 50-fold sample dilution (0.5 g sample extraction to 25 mL sample final volume). The precision, expressed as a relative standard deviation (% RSD, n=10), was 0.2% for both selenium and arsenic in 200 microg L(-1) solutions, which corresponds to 10 microg g(-1) in sediment samples after acid extraction. Applying the proposed procedure, a linear range of 0.08-10 and 0.10-10 microg g(-1) was obtained for selenium and arsenic, respectively. The developed procedure was validated by the analysis of two certified reference materials: industrial sludge (NIST 2782) and river sediment (NIST 8704). The results were in agreement with the certified values. The developed procedure was applied to evaluate the bioavailability of both elements in four sediment certified reference materials, in which there are not certified values for bioavailable fractions, and also in estuarine sediment samples collected in several sites of Guanabara Bay, an impacted environment in Rio de Janeiro, Brazil.

Hydrogen and dihydrogen bonding of transition metal hydrides

NASA Astrophysics Data System (ADS)

Jacobsen, Heiko

2008-04-01

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

On-line pre-reduction of Se(VI) by thiourea for selenium speciation by hydride generation

NASA Astrophysics Data System (ADS)

Qiu, Jianhua; Wang, Qiuquan; Ma, Yuning; Yang, Limin; Huang, Benli

2006-07-01

In this study, thiourea (TU) was novelly developed as a reduction reagent for on-line pre-reduction of selenium(VI) before conventional hydride generation (HG) by KBH 4/NaOH-HCl. After TU on-line pre-reduction, the HG efficiency of Se(VI) has been greatly improved and because even higher than that of the same amount of Se(IV) obtained in the conventional HG system. The possible pre-reduction mechanism is discussed. The detection limit (DL) of selenate reaches 10 pg mL - 1 when using on-line TU pre-reduction followed by HG atomic fluorescence detection. When TU pre-reduction followed by HG is used as an interface between ion-pair high performance liquid chromatography and atomic fluorescence spectrometry, selenocystine, selenomethionine, selenite and selenate can be measured simultaneously and quantitatively. The DLs of these are 0.06, 0.08, 0.05 and 0.04 ng mL - 1 , respectively, and the relative standard deviations of 9 duplicate runs for all the 4 species are less than 5%. Furthermore, it was successfully applied to Se speciation analysis of cultured garlic samples, and validated by determination of total selenium and selenium species in certified reference material NIST 1946.

Regenerative Hydride Heat Pump

NASA Technical Reports Server (NTRS)

Jones, Jack A.

1992-01-01

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

[Fluorescence Determination of Trace Se with the Hydride-K13-Rhodamine 6G System].

PubMed

Liang, Ai-hui; Li, Yuan; Huang, Shan-shan; Luo, Yang-he; Wen, Gui-qing; Jiang, Zhi-liang

2015-05-01

Se is a necessary trace element for human and animals, but the excess intake of Se caused poison. Thus, it is very important to determination of Se in foods and water. The target of this study is development of a new, sensitive and selective hydride generation-molecular fluorescence method for the determination of Se. In 0. 36 mol . L-1 sulfuric acid, NaBH4 as reducing agent, Se (IV) is reduced to H2 Se. Usin3-g I solution as absorption liquid3, I- is reduced to I- by H2Se. When adding rhodamine 6G, Rhodamine 6G and I3- form association particles, which lead to the fluorescence intensity decreased. When Se(IV) existing, Rhodamine 6G and I3- bind less, And the remaining amount of Rhodamine 6G increase. So the fluorescence intensity is enhanced. The analytical conditions were optimized, a 0. 36 ml . L-1 H2SO4, 21. 6.g . L-1 NaBH4, 23.3 µm . L-1 rhodamine 6G, and 50 µmol . L-1 KI3 were chosen for use. When the excitation wavelength is at 480nm, the Rayleigh scattering peak does not affect the fluorescence recording, and was selected for determination of Se. Under the selected conditions, Se(IV) concentration in the 0. 02~0. 60 µg . mL-1 range and the increase value of the fluorescence intensity (ΔF) at 562 nm linear relationship. The linear regression equation is ΔF562 nm =12. 6c + 20. 9. The detecton limit was 0.01 µ.g . L-1. The influence of coexistence substances on the hydride generatin-molecular fluorescence determination of 5. 07 X10(-6) mol . L-1 Se(IV) was considered in details. Results showed that this new fluorescence method is of high selectivity, that is, 0. 5 mmol. L-1 Ba2+, Ca2+, Zn2+ and Fe3+, 0. 25 mmol . L-1 . Mg2+, 0. 05 mmol . L-1 K+, 0. 2 mmol . L-1 Al3+, 0. 025 mmol . L-1 Te(VI) do not interfere with the determination. The influence of Hg2+, CD2+ and Cu2+ that precipitate with Se(IV), can be eliminated by addition of complex reagent. This hydride generation-molecular fluorescence method has been applied to determination of trace Se in water

Automated system for on-line determination of dimethylarsinic and inorganic arsenic by hydride generation-atomic fluorescence spectrometry.

PubMed

Chaparro, L L; Ferrer, L; Cerdà, V; Leal, L O

2012-09-01

A multisyringe flow-injection approach has been coupled to hydride generation-atomic fluorescence spectrometry (HG-AFS) with UV photo-oxidation for dimethylarsinic (DMA), inorganic As and total As determination, depending on the pre-treatment given to the sample (extraction or digestion). The implementation of a UV lamp allows on-line photo-oxidation of DMA and the following arsenic detection, whereas a bypass leads the flow directly to the HG-AFS system, performing inorganic arsenic determination. DMA concentration is calculated by the difference of total inorganic arsenic and measurement of the photo-oxidation step. The detection limits for DMA and inorganic arsenic were 0.09 and 0.47 μg L(-1), respectively. The repeatability values accomplished were of 2.4 and 1.8%, whereas the injection frequencies were 24 and 28 injections per hour for DMA and inorganic arsenic, respectively. This method was validated by means of a solid reference material BCR-627 (muscle of tuna) with good agreement with the certified values. Satisfactory results for DMA and inorganic arsenic determination were obtained in several water matrices. The proposed method offers several advantages, such as increasing the sampling frequency, low detection limits and decreasing reagents and sample consumption, which leads to lower waste generation.

On the Chemistry of Hydrides of N Atoms and O+ Ions

NASA Astrophysics Data System (ADS)

Awad, Zainab; Viti, Serena; Williams, David A.

2016-08-01

Previous work by various authors has suggested that the detection by Herschel/HIFI of nitrogen hydrides along the low-density lines of sight toward G10.6-0.4 (W31C) cannot be accounted for by gas-phase chemical models. In this paper we investigate the role of surface reactions on dust grains in diffuse regions, and we find that formation of the hydrides by surface reactions on dust grains with efficiency comparable to that for H2 formation reconciles models with observations of nitrogen hydrides. However, similar surface reactions do not contribute significantly to the hydrides of O+ ions detected by Herschel/HIFI that are present along many sight lines in the Galaxy. The O+ hydrides can be accounted for by conventional gas-phase chemistry either in diffuse clouds of very low density with normal cosmic-ray fluxes or in somewhat denser diffuse clouds with high cosmic-ray fluxes. Hydride chemistry in dense dark clouds appears to be dominated by gas-phase ion-molecule reactions.

Zirconium Hydride Space Power Reactor design.

NASA Technical Reports Server (NTRS)

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

1972-01-01

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

Effect of hydrogenation conditions on the microstructure and mechanical properties of zirconium hydride

NASA Astrophysics Data System (ADS)

Muta, Hiroaki; Nishikane, Ryoji; Ando, Yusuke; Matsunaga, Junji; Sakamoto, Kan; Harjo, Stefanus; Kawasaki, Takuro; Ohishi, Yuji; Kurosaki, Ken; Yamanaka, Shinsuke

2018-03-01

Precipitation of brittle zirconium hydrides deteriorate the fracture toughness of the fuel cladding tubes of light water reactor. Although the hydride embrittlement has been studied extensively, little is known about physical properties of the hydride due to the experimental difficulties. In the present study, to elucidate relationship between mechanical properties and microstructure, two δ-phase zirconium hydrides and one ε-phase zirconium hydride were carefully fabricated considering volume changes at the metal-to-hydride transformation. The δ-hydride that was fabricated from α-zirconium exhibits numerous inner cracks due to the large volume change. Analyses of the neutron diffraction pattern and electron backscatter diffraction (EBSD) data show that the sample displays significant stacking faults in the {111} plane and in the pseudo-layered microstructure. On the other hand, the δ-hydride sample fabricated from β-zirconium at a higher temperature displays equiaxed grains and no cracks. The strong crystal orientation dependence of mechanical properties were confirmed by indentation test and EBSD observation. The δ-hydride hydrogenated from α-zirconium displays a lower Young's modulus than that prepared from β-zirconium. The difference is attributed to stacking faults within the {111} plane, for which the Young's modulus exhibits the highest value in the perpendicular direction. The strong influence of the crystal orientation and dislocation density on the mechanical properties should be considered when evaluating hydride precipitates in nuclear fuel cladding.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zidan, Ragaiy; Hardy, B. J.; Corgnale, C.

2016-01-31

The objective of this research was to evaluate and demonstrate a metal hydride-based TES system for use with a CSP system. A unique approach has been applied to this project that combines our modeling experience with the extensive material knowledge and expertise at both SRNL and Curtin University (CU). Because of their high energy capacity and reasonable kinetics many metal hydride systems can be charged rapidly. Metal hydrides for vehicle applications have demonstrated charging rates in minutes and tens of minutes as opposed to hours. This coupled with high heat of reaction allows metal hydride TES systems to produce verymore » high thermal power rates (approx. 1kW per 6-8 kg of material). A major objective of this work is to evaluate some of the new metal hydride materials that have recently become available. A problem with metal hydride TES systems in the past has been selecting a suitable high capacity low temperature metal hydride material to pair with the high temperature material. A unique aspect of metal hydride TES systems is that many of these systems can be located on or near dish/engine collectors due to their high thermal capacity and small size. The primary objective of this work is to develop a high enthalpy metal hydride that is capable of reversibly storing hydrogen at high temperatures (> 650 °C) and that can be paired with a suitable low enthalpy metal hydride with low cost materials. Furthermore, a demonstration of hydrogen cycling between the two hydride beds is desired.« less

Precipitation of hydrides in high purity niobium after different treatments

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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

Neutron diffraction investigation of γ manganese hydride

NASA Astrophysics Data System (ADS)

Fedotov, V. K.; Antonov, V. E.; Kolesnikov, A. I.; Beskrovnyi, A. I.; Grosse, G.; Wagner, F. E.

1998-08-01

A profile analysis of the neutron diffraction spectrum of the fcc high pressure hydride λ-MnH 0.41 measured under ambient conditions showed that hydrogen is randomly distributed over the octahedral interstices of the fcc metal lattice and that the hydride is an antiferromagnet with the same collinear spin structure as pure λ-Mn, but with a smaller magnetic moment of about 1.9 Bohr magnetons per Mn atom.

Evaluation of methods for trace-element determination with emphasis on their usability in the clinical routine laboratory.

PubMed

Bolann, B J; Rahil-Khazen, R; Henriksen, H; Isrenn, R; Ulvik, R J

2007-01-01

Commonly used techniques for trace-element analysis in human biological material are flame atomic absorption spectrometry (FAAS), graphite furnace atomic absorption spectrometry (GFAAS), inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). Elements that form volatile hydrides, first of all mercury, are analysed by hydride generation techniques. In the absorption techniques the samples are vaporized into free, neutral atoms and illuminated by a light source that emits the atomic spectrum of the element under analysis. The absorbance gives a quantitative measure of the concentration of the element. ICP-AES and ICP-MS are multi-element techniques. In ICP-AES the atoms of the sample are excited by, for example, argon plasma at very high temperatures. The emitted light is directed to a detector, and the optical signals are processed to values for the concentrations of the elements. In ICP-MS a mass spectrometer separates and detects ions produced by the ICP, according to their mass-to-charge ratio. Dilution of biological fluids is commonly needed to reduce the effect of the matrix. Digestion using acids and microwave energy in closed vessels at elevated pressure is often used. Matrix and spectral interferences may cause problems. Precautions should be taken against trace-element contamination during collection, storage and processing of samples. For clinical problems requiring the analysis of only one or a few elements, the use of FAAS may be sufficient, unless the higher sensitivity of GFAAS is required. For screening of multiple elements, however, the ICP techniques are preferable.

On the coupling of hydride generation with atmospheric pressure glow discharge in contact with the flowing liquid cathode for the determination of arsenic, antimony and selenium with optical emission spectrometry.

PubMed

Greda, Krzysztof; Jamroz, Piotr; Jedryczko, Dominika; Pohl, Pawel

2015-05-01

The miniaturized atmospheric pressure glow discharge (APGD) sustained between a liquid flowing cathode and a He nozzle jet anode was combined with hydride generation (HG) to improve the performance of the determination of As, Sb and Se with optical emission spectrometry (OES). As(III), Sb(III) and Se(IV) species were converted into volatile hydrides in the reaction with NaBH4 and right after that they were delivered to the near-anode region of APGD through the nozzle. The transport efficiency of As, Sb and Se to the discharge was several times higher, while intensities of atomic emission lines of As, Sb and Se were improved 3 orders of magnitude (as compared to intensities acquired for the near-cathode region in a APGD system with a typical introduction of analytes through sputtering of the flowing liquid cathode). The effect of the concentration of NaBH4 and HCl in a sample solution, the discharge current, the flow rate of He carrier/jet-supporting and He shielding gases on the emission yield coming from As, Sb, Se, He and H atomic lines and OH and N2 band heads as well as the electron number density was thoroughly studied. Under compromised conditions, limits of detection (3σ criterion) of As, Sb and Se were respectively 4.2, 1.2 and 3.1 µg L(-1). Usefulness of the method was confirmed by the analysis of Sniadecki and Marchlewski highly mineralized spring waters (Kudowa Zdroj, Poland) on the content of As, Sb and Se. Recoveries of elements added to these spring waters were within 90.3-103.7% proving good accuracy of the HG-APGD-OES method. Copyright © 2015 Elsevier B.V. All rights reserved.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tummala, Hareesh; Capolungo, Laurent; Tome, Carlos N.

This report is a preliminary study on δ-hydride precipitate in zirconium alloy performed using 3D discrete dislocation dynamics simulations. The ability of dislocations in modifying the largely anisotropic stress fields developed by the hydride particle in a matrix phase is addressed for a specific dimension of the hydride. The influential role of probable dislocation nucleation at the hydride-matrix interface is reported. Dislocation nucleation around a hydride was found to decrease the shear stress (S 13) and also increase the normal stresses inside the hydride. We derive conclusions on the formation of stacks of hydrides in zirconium alloys. The contribution ofmore » mechanical fields due to dislocations was found to have a non-negligible effect on such process.« less

Placing three-dimensional isoparametric elements into NASTRAN. [alterations in matrix assembly to simplify generation of higher order elements

NASA Technical Reports Server (NTRS)

Newman, M. B.; Filstrup, A. W.

1973-01-01

Linear (8 node), parabolic (20 node), cubic (32 node) and mixed (some edges linear, some parabolic and some cubic) have been inserted into NASTRAN, level 15.1. First the dummy element feature was used to check out the stiffness matrix generation routines for the linear element in NASTRAN. Then, the necessary modules of NASTRAN were modified to include the new family of elements. The matrix assembly was changed so that the stiffness matrix of each isoparametric element is only generated once as the time to generate these higher order elements tends to be much longer than the other elements in NASTRAN. This paper presents some of the experiences and difficulties of inserting a new element or family of elements into NASTRAN.

Mixed Element Type Unstructured Grid Generation for Viscous Flow Applications

NASA Technical Reports Server (NTRS)

Marcum, David L.; Gaither, J. Adam

2000-01-01

A procedure is presented for efficient generation of high-quality unstructured grids suitable for CFD simulation of high Reynolds number viscous flow fields. Layers of anisotropic elements are generated by advancing along prescribed normals from solid boundaries. The points are generated such that either pentahedral or tetrahedral elements with an implied connectivity can be be directly recovered. As points are generated they are temporarily attached to a volume triangulation of the boundary points. This triangulation allows efficient local search algorithms to be used when checking merging layers, The existing advancing-front/local-reconnection procedure is used to generate isotropic elements outside of the anisotropic region. Results are presented for a variety of applications. The results demonstrate that high-quality anisotropic unstructured grids can be efficiently and consistently generated for complex configurations.

LaNi{sub 5}-based metal hydride electrode in Ni-MH rechargeable cells

DOEpatents

Bugga, R.V.; Fultz, B.; Bowman, R.; Surampudi, S.R.; Witham, C.K.; Hightower, A.

1999-03-30

An at least ternary metal alloy of the formula AB{sub (Z-Y)}X{sub (Y)} is disclosed. 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, germanium, tin or bismuth. Z is greater than or equal to 4.8 and less than or equal to 6.0. Y is greater than 0 and less than 1. 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. 16 figs.

Determination of arsenite, arsenate, monomethylarsonic acid and dimethylarsinic acid in cereals by hydride generation atomic fluorescence spectrometry

NASA Astrophysics Data System (ADS)

Matos Reyes, M. N.; Cervera, M. L.; Campos, R. C.; de la Guardia, M.

2007-09-01

A fast, sensitive and simple non-chromatographic analytical method was developed for the speciation analysis of toxic arsenic species in cereal samples, namely rice and wheat semolina. An ultrasound-assisted extraction of the toxic arsenic species was performed with 1 mol L - 1 H 3PO 4 and 0.1% (m/v) Triton XT-114. After extraction, As(III), As(V), dimethylarsinic acid (DMA) and monomethylarsonic acid (MMA) concentrations were determined by hydride generation atomic fluorescence spectrometry using a series of proportional equations corresponding to four different experimental reduction conditions. The detection limits of the method were 1.3, 0.9, 1.5 and 0.6 ng g - 1 for As(III), As(V), DMA and MMA, respectively, expressed in terms of sample dry weight. Recoveries were always greater than 90%, and no species interconversion occurred. The speciation analysis of a rice flour reference material certified for total arsenic led to coherent results, which were also in agreement with other speciation studies made on the same certified reference material.

Effects on the positive electrode of the corrosion of AB{sub 5} alloys in nickel-metal-hydride batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bernard, P.

1998-02-01

Effects of corrosion of MmNi{sub 4.3{minus}x}Mn{sub 0.3}Al{sub 0.4}Co{sub x} alloys (where Mm = Ce 50%, La 30%, Nd 15%, Pr 5%) are evaluated in nickel-metal-hydride (Ni-MH) cells. Particularly, it is shown how Al released by the corroded alloys pollutes the positive electrode, which endures a loss of charging efficiency, due to the formation of a hydrotalcite-like phase stabilized with Al. Furthermore, since Al is eluted from the hydride electrode and is completely trapped in the positive active material, the titration of this element in the positive electrode is a powerful technique for quantification of the corrosion of AB{sub 5} alloysmore » in Ni-MH cells.« less

Improved acid digestion of environmental and biological samples and coal for the determination of both arsenic and selenium by hydride generation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Z.

1994-12-31

Hydride generation (HG) is a good sample introduction technique for the determination of As and Se, and has been widely used in atomic spectrometry. Several instrumental developments have been made in the hydride-generation system, however, sample digestion (pretreatment) is still the critical step in the FIG determination of As and Se in solid and semi-solid samples. The general digestion procedure with mineral acids is not suitable for complete decomposition of refractory organic compounds of As and Se present in some organic-rich materials, and then does not allow for the measurement of both As and Se in most environmental and biologicalmore » samples by HG. In this work, some well-designed experiments on the wet digestion in open system have been done with a temperature controlled sand bath. The oxidation performances of some mixtures of mineral acids and salts in different combinations have been investigated and evaluated with environmental and biological samples. With the use of HNO{sub 3}/HClO{sub 4} mixing with either the high-boiling-point acids (H{sub 2}SO{sub 4}, H{sub 3}PO{sub 4}) or some mineral salts(Mg(NO{sub 3}){sub 2}, MgSO{sub 4}, Na{sub 2}SO{sub 4}, NaH{sub 2}PO{sub 4}), the complete mineralization of organoarsenic and organoselenium compounds in the samples can be readily achieved while a dewatered step is in the employ of the digestion program. An improved wet digestion procedure with HNO{sub 3}/HClO{sub 4}/H{sub 3}PO{sub 4}(or Mg(NO{sub 3}){sub 2}, or MgSO{sub 4}) was investigated and optimized for the determination of both As and Se in sediment, soil, coal, fish and plant materials by HG-AAS. This method has been evaluated by the analyses of CRMs, including PACS-1, BCSS-1, MESS-11 DORM-1. DOLT-1. NIST-1632b, BCR-40 and BCR-181 for both As and Se, and good agreements with the certified values were obtained.« less

Molecular modeling of the reaction pathway and hydride transfer reactions of HMG-CoA reductase.

PubMed

Haines, Brandon E; Steussy, C Nicklaus; Stauffacher, Cynthia V; Wiest, Olaf

2012-10-09

HMG-CoA reductase catalyzes the four-electron reduction of HMG-CoA to mevalonate and is an enzyme of considerable biomedical relevance because of the impact of its statin inhibitors on public health. Although the reaction has been studied extensively using X-ray crystallography, there are surprisingly no computational studies that test the mechanistic hypotheses suggested for this complex reaction. Theozyme and quantum mechanical (QM)/molecular mechanical (MM) calculations up to the B3LYP/6-31g(d,p)//B3LYP/6-311++g(2d,2p) level of theory were employed to generate an atomistic description of the enzymatic reaction process and its energy profile. The models generated here predict that the catalytically important Glu83 is protonated prior to hydride transfer and that it acts as the general acid or base in the reaction. With Glu83 protonated, the activation energies calculated for the sequential hydride transfer reactions, 21.8 and 19.3 kcal/mol, are in qualitative agreement with the experimentally determined rate constant for the entire reaction (1 s(-1) to 1 min(-1)). When Glu83 is not protonated, the first hydride transfer reaction is predicted to be disfavored by >20 kcal/mol, and the activation energy is predicted to be higher by >10 kcal/mol. While not involved in the reaction as an acid or base, Lys267 is critical for stabilization of the transition state in forming an oxyanion hole with the protonated Glu83. Molecular dynamics simulations and MM/Poisson-Boltzmann surface area free energy calculations predict that the enzyme active site stabilizes the hemithioacetal intermediate better than the aldehyde intermediate. This suggests a mechanism in which cofactor exchange occurs before the breakdown of the hemithioacetal. Slowing the conversion to aldehyde would provide the enzyme with a mechanism to protect it from solvent and explain why the free aldehyde is not observed experimentally. Our results support the hypothesis that the pK(a) of an active site acidic

First-Principles Modeling of Hydrogen Storage in Metal Hydride Systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

J. Karl Johnson

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. Newmore » 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.« less

Metal hydride-based thermal energy storage systems

DOEpatents

Vajo, John J.; Fang, Zhigang

2017-10-03

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

CO2 hydrogenation on a metal hydride surface.

PubMed

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

2012-04-28

The catalytic hydrogenation of CO(2) at the surface of a metal hydride and the corresponding surface segregation were investigated. The surface processes on Mg(2)NiH(4) were analyzed by in situ X-ray photoelectron spectroscopy (XPS) combined with thermal desorption spectroscopy (TDS) and mass spectrometry (MS), and time-of-flight secondary ion mass spectrometry (ToF-SIMS). CO(2) hydrogenation on the hydride surface during hydrogen desorption was analyzed by catalytic activity measurement with a flow reactor, a gas chromatograph (GC) and MS. We conclude that for the CO(2) methanation reaction, the dissociation of H(2) molecules at the surface is not the rate controlling step but the dissociative adsorption of CO(2) molecules on the hydride surface. This journal is © the Owner Societies 2012

Technical and economic aspects of hydrogen storage in metal hydrides

NASA Technical Reports Server (NTRS)

Schmitt, R.

1981-01-01

The recovery of hydrogen from such metal hydrides as LiH, MgH2, TiH2, CaH2 and FeTiH compounds is studied, with the aim of evaluating the viability of the technique for the storage of hydrogen fuel. The pressure-temperature dependence of the reactions, enthalpies of formation, the kinetics of the hydrogen absorption and desorption, and the mechanical and chemical stability of the metal hydrides are taken into account in the evaluation. Economic aspects are considered. Development of portable metal hydride hydrogen storage reservoirs is also mentioned.

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

NASA Astrophysics Data System (ADS)

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

LaNi{sub 5}-based metal hydride electrode in Ni-MH rechargeable cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bugga, R.V.; Fultz, B.; Bowman, R.

1999-03-30

An at least ternary metal alloy of the formula AB{sub (Z-Y)}X{sub (Y)} is disclosed. 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, germanium, tin or bismuth. Z is greater than or equal to 4.8 and less than or equal to 6.0. Y is greater than 0 and less than 1. Ternary or higher-order substitutions to the base AB{sub 5} alloys that form strong kinetic interactions with themore » predominant metals in the base metal hydride are used to form metal alloys with high structural integrity after multiple cycles of hydrogen sorption. 16 figs.« less

Photoconductive circuit element pulse generator

DOEpatents

Rauscher, Christen

1989-01-01

A pulse generator for characterizing semiconductor devices at millimeter wavelength frequencies where a photoconductive circuit element (PCE) is biased by a direct current voltage source and produces short electrical pulses when excited into conductance by short laser light pulses. The electrical pulses are electronically conditioned to improve the frequency related amplitude characteristics of the pulses which thereafter propagate along a transmission line to a device under test.

LaNi.sub.5 is-based metal hydride electrode in Ni-MH rechargeable cells

DOEpatents

Bugga, Ratnakumar V.; Fultz, Brent; Bowman, Robert; Surampudi, Subra Rao; Witham, Charles K.; Hightower, Adrian

1999-01-01

An at least ternary metal alloy of the formula AB.sub.(Z-Y) X.sub.(Y) is disclosed. 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, germanium, tin or bismuth. Z is greater than or equal to 4.8 and less than or equal to 6.0. Y is greater than 0 and less than 1. 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.

Synthesis and hydriding properties of Li 2Mg(NH) 2

NASA Astrophysics Data System (ADS)

Markmaitree, Tippawan; Shaw, Leon L.

The phase pure Li 2Mg(NH) 2 has been synthesized via a dehydriding treatment of a ball milled 2LiNH 2 + MgH 2 mixture. This phase pure Li 2Mg(NH) 2 has been utilized to investigate its hydriding kinetics at the temperature range 180-220 °C. It is found that the hydriding process of Li 2Mg(NH) 2 is very sluggish even though it has favorable thermodynamic properties for near the ambient temperature operation. Holding at 200 °C for 10 h only results in 3.75 wt.% H 2 uptake. The detailed kinetic analysis reveals that the hydriding process of Li 2Mg(NH) 2 is diffusion-controlled. Thus, this study unambiguously indicates that the future direction to enhance the hydriding kinetics of this promising hydrogen storage material system should be to minimize the diffusion distance and increase the diffusion rate.

Hydrogen transmission/storage with a metal hydride/organic slurry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Breault, R.W.; Rolfe, J.; McClaine, A.

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:more » 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.« less

Super Hydrides.

DTIC Science & Technology

1988-03-01

enantioselective synthesis Of the clinically important anti-depressants, (-)Tomoxetine, Fluoxetine (Prozac, Eli Lilly), and Nisoxetine (Scheme 1 ). Schem I a I...Scheme 1 . Another salient feature of this synthesis is that it correlated for the first time the absolute configuration of the enantiomers of...RD-RI93 710 SUPER HYDRIDES(U) PURDUE UNIV LRFRYETTE IN H C BROWN 1 / 1 NAR 88 RRO-22302.2-CN DAR29-05-K-1662 UNCLSSIFIED F/G 7/3 NI. t2S 16, L,. 10 3

[Microsecond Pulsed Hollow Cathode Lamp as Enhanced Excitation Source of Hydride Generation Atomic Fluorescence Spectrometry].

PubMed

Zhang, Shuo

2015-09-01

The spectral, electrical and atomic fluorescence characteristics of As, Se, Sb and Pb hollow cathode lamps (HCLs) powered by a laboratory-built high current microsecond pulse (HCMP) power supply were studied, and the feasibility of using HCMP-HCLs as the excitation source of hydride generation atomic fluorescence spectrometry (HG-AFS) was evaluated. Under the HCMP power supply mode, the As, Se, Sb, Pb HCLs can maintain stable glow discharge at frequency of 100~1000 Hz, pulse width of 4.0~20 μs and pulse current up to 4.0 A. Relationship between the intensity of characteristic emission lines and HCMP power supply parameters, such as pulse current, power supply voltage, pulse width and frequency, was studied in detail. Compared with the conventional pulsed (CP) HCLs used in commercial AFS instruments, HCMP-HCLs have a narrower pulse width and much stronger pulse current. Under the optimized HCMP power supply parameters, the intensity of atomic emission lines of As, Se, Sb HCLs had sharp enhancement and that indicated their capacity of being a novel HG-AFS excitation source. However, the attenuation of atomic lines and enhancement of ionic lines negated such feasibility of HCMP-Pb HCL. Then the HG-AFS analytical capability of using the HCMP-As/Se/Sb HCLs excitation source was established and results showed that the HCMP-HCL is a promising excitation source for HG-AFS.

Method of selective reduction of halodisilanes with alkyltin hydrides

DOEpatents

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.

Hydride Molecules towards Nearby Galaxies

NASA Astrophysics Data System (ADS)

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

2018-06-01

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

DEVELOPMENT OF A FABRICATION PROCESS FOR SOL-GEL/METAL HYDRIDE COMPOSITE GRANULES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hansen, E; Eric Frickey, E; Leung Heung, L

An external gelation process was developed to produce spherical granules that contain metal hydride particles in a sol-gel matrix. Dimensionally stable granules containing metal hydrides are needed for applications such as hydrogen separation and hydrogen purification that require columns containing metal hydrides. Gases must readily flow through the metal hydride beds in the columns. Metal hydrides reversibly absorb and desorb hydrogen and hydrogen isotopes. This is accompanied by significant volume changes that cause the metal hydride to break apart or decrepitate. Repeated cycling results in very fine metal hydride particles that are difficult to handle and contain. Fine particles tendmore » to settle and pack making it more difficult to flow gases through a metal hydride bed. Furthermore, the metal hydrides can exert a significant force on the containment vessel as they expand. These problems associated with metal hydrides can be eliminated with the granulation process described in this report. Small agglomerates of metal hydride particles and abietic acid (a pore former) were produced and dispersed in a colloidal silica/water suspension to form the feed slurry. Fumed silica was added to increase the viscosity of the feed slurry which helped to keep the agglomerates in suspension. Drops of the feed slurry were injected into a 27-foot tall column of hot ({approx}70 C), medium viscosity ({approx}3000 centistokes) silicone oil. Water was slowly evaporated from the drops as they settled. The drops gelled and eventually solidified to form spherical granules. This process is referred to as external gelation. Testing was completed to optimize the design of the column, the feed system, the feed slurry composition, and the operating parameters of the column. The critical process parameters can be controlled resulting in a reproducible fabrication technique. The residual silicone oil on the surface of the granules was removed by washing in mineral spirits. The granules

Composite Materials for Hazard Mitigation of Reactive Metal Hydrides.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pratt, Joseph William; Cordaro, Joseph Gabriel; Sartor, George B.

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 heatmore » 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

Mössbauer studies of iron hydride at high pressure

NASA Astrophysics Data System (ADS)

Choe, I.; Ingalls, R.; Brown, J. M.; Sato-Sorensen, Y.; Mills, R.

1991-07-01

We have measured in situ Mössbauer spectra of iron hydride made in a diamond anvil cell at high pressure and room temperature. The spectra show a sudden change at 3.5+/-0.5 GPa from a single hyperfine pattern to a superposition of three. The former pattern results from normal α-iron with negligible hydrogen content, and the latter from residual α-iron plus newly formed iron hydride. Between 3.5 and 10.4 GPa, the extra hydride pattern have hyperfine fields for one ranging from 276 to 263 kOe, and the other, from 317 to 309 kOe. Both have isomer shifts of about 0.4 mm/sec, and negligible quadrupole splittings. X-ray studies on quenched samples have shown that iron hydride is of double hexagonal close-packed structure, whose two nonequivalent iron sites may account for the observation of two different patterns. Even allowing for the effect of volume expansion, the observed isomer shifts for the hydride are considerably more positive than those of other metallic phases of iron. At the same time, the hyperfine fields are slightly smaller than that of α-iron. As a possible explanation, one may expect a bonding of hydrogen with iron, which would result in a small reduction of 4s electrons, possibly accompanied by a small increase of 3d electrons compared with the neutral atom in metallic iron. The difference between the hyperfine fields in the two spectra are presumably due to the different symmetry at the two iron sites.

Hydrogen-storing hydride complexes

DOEpatents

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

2012-04-10

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

Selective determination of four arsenic species in rice and water samples by modified graphite electrode-based electrolytic hydride generation coupled with atomic fluorescence spectrometry.

PubMed

Yang, Xin-An; Lu, Xiao-Ping; Liu, Lin; Chi, Miao-Bin; Hu, Hui-Hui; Zhang, Wang-Bing

2016-10-01

This work describes a novel non-chromatographic approach for the accurate and selective determining As species by modified graphite electrode-based electrolytic hydride generation (EHG) for sample introduction coupled with atomic fluorescence spectrometry (AFS) detection. Two kinds of sulfydryl-containing modifiers, l-cysteine (Cys) and glutathione (GSH), are used to modify cathode. The EHG performance of As has been changed greatly at the modified cathode, which has never been reported. Arsenite [As(III)] on the GSH modified graphite electrode (GSH/GE)-based EHG can be selectively and quantitatively converted to AsH3 at applied current of 0.4A. As(III) and arsenate [As(V)] on the Cys modified graphite electrode (Cys/GE) EHG can be selectively and efficiently converted to arsine at applied current of 0.6A, whereas monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) do not form any or only less volatile hydrides under this condition. By changing the analytical conditions, we also have achieved the analysis of total As (tAs) and DMA. Under the optimal condition, the detection limits (3s) of As(III), iAs and tAs in aqueous solutions are 0.25μgL(-1), 0.22μgL(-1) and 0.10μgL(-1), respectively. The accuracy of the method is verified through the analysis of standard reference materials (SRM 1568a). Copyright © 2016 Elsevier B.V. All rights reserved.

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

PubMed Central

Oumellal, Yassine; Bonnet, Jean-Pierre

2015-01-01

Summary The state of the art of conversion reactions of metal hydrides (MH) with lithium is presented and discussed in this review with regard to the use of these hydrides as anode materials for lithium-ion batteries. A focus on the gravimetric and volumetric storage capacities for different examples from binary, ternary and complex hydrides is presented, with a comparison between thermodynamic prediction and experimental results. MgH2 constitutes one of the most attractive metal hydrides with a reversible capacity of 1480 mA·h·g−1 at a suitable potential (0.5 V vs Li+/Li0) and the lowest electrode polarization (<0.2 V) for conversion materials. Conversion process reaction mechanisms with lithium are subsequently detailed for MgH2, TiH2, complex hydrides Mg2MHx and other Mg-based hydrides. The reversible conversion reaction mechanism of MgH2, which is lithium-controlled, can be extended to others hydrides as: MHx + xLi+ + xe− in equilibrium with M + xLiH. Other reaction paths—involving solid solutions, metastable distorted phases, and phases with low hydrogen content—were recently reported for TiH2 and Mg2FeH6, Mg2CoH5 and Mg2NiH4. The importance of fundamental aspects to overcome technological difficulties is discussed with a focus on conversion reaction limitations in the case of MgH2. The influence of MgH2 particle size, mechanical grinding, hydrogen sorption cycles, grinding with carbon, reactive milling under hydrogen, and metal and catalyst addition to the MgH2/carbon composite on kinetics improvement and reversibility is presented. Drastic technological improvement in order to the enhance conversion process efficiencies is needed for practical applications. The main goals are minimizing the impact of electrode volume variation during lithium extraction and overcoming the poor electronic conductivity of LiH. To use polymer binders to improve the cycle life of the hydride-based electrode and to synthesize nanoscale composite hydride can be helpful to

Method of selective reduction of polyhalosilanes with alkyltin hydrides

DOEpatents

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

1989-01-01

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

Simultaneous plate forming and hydriding of La(Fe, Si)13 magnetocaloric powders

NASA Astrophysics Data System (ADS)

Yang, Nannan; You, Caiyin; Tian, Na; Zhang, Yue; Leng, Haiyan; He, Jun

2018-04-01

In this work, we propose a way to simultaneously realize the plate forming and hydriding of La(Fe, Si)13 powders by mixing hydride MgNiYHx and solder powders Sn3.0Ag0.5Cu. Under the annealing of the green compact, the hydriding of La(Fe, Si)13 was realized through absorbing the released hydrogen from the metallic hydride MgNiYHx. The Curie temperature of La(Fe, Si)13 alloy increased from 213 K to 333 K and hysteresis reduced from 3.3 J/kg·K to 1.33 J/kg·K. Due to the bonding of Sn3.0Ag0.5Cu powders, the mechanical strength of the composite compact was highly improved in comparison to the compact of La(Fe, Si)13 powders alone.

A benign synthesis of alane by the composition-controlled mechanochemical reaction of sodium hydride and aluminum chloride

DOE PAGES

Hlova, Ihor; Goldston, Jennifer F.; Gupta, Shalabh; ...

2017-05-30

Solid-state mechanochemical synthesis of alane (AlH 3) starting from sodium hydride (NaH) and aluminum chloride (AlCl 3) has been achieved at room temperature. The transformation pathway of this solid-state reaction was controlled by a stepwise addition of AlCl 3 to the initial reaction mixture that contained sodium hydride in excess of stoichiometric amount. As in the case of previously investigated LiH–AlCl 3 system, complete selectivity was achieved whereby formation of unwanted elemental aluminum was fully suppressed, and AlH 3 was obtained in quantitative yield. Reaction progress during each step was investigated by means of solid-state NMR and powder X-ray diffraction,more » which revealed that the overall reaction proceeds through a series of intermediate alanates that may be partially chlorinated. The NaH–AlCl 3 system presents some subtle differences compared to LiH–AlCl 3 system particularly with respect to optimal concentrations needed during one of the reaction stages. Based on the results, we postulate that high local concentrations of NaH may stabilize chlorine-containing derivatives and prevent decomposition into elemental aluminum with hydrogen evolution. As a result, complete conversion with quantitative yield of alane was confirmed by both SSNMR and hydrogen desorption analysis.« less

A benign synthesis of alane by the composition-controlled mechanochemical reaction of sodium hydride and aluminum chloride

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hlova, Ihor; Goldston, Jennifer F.; Gupta, Shalabh

Solid-state mechanochemical synthesis of alane (AlH 3) starting from sodium hydride (NaH) and aluminum chloride (AlCl 3) has been achieved at room temperature. The transformation pathway of this solid-state reaction was controlled by a stepwise addition of AlCl 3 to the initial reaction mixture that contained sodium hydride in excess of stoichiometric amount. As in the case of previously investigated LiH–AlCl 3 system, complete selectivity was achieved whereby formation of unwanted elemental aluminum was fully suppressed, and AlH 3 was obtained in quantitative yield. Reaction progress during each step was investigated by means of solid-state NMR and powder X-ray diffraction,more » which revealed that the overall reaction proceeds through a series of intermediate alanates that may be partially chlorinated. The NaH–AlCl 3 system presents some subtle differences compared to LiH–AlCl 3 system particularly with respect to optimal concentrations needed during one of the reaction stages. Based on the results, we postulate that high local concentrations of NaH may stabilize chlorine-containing derivatives and prevent decomposition into elemental aluminum with hydrogen evolution. As a result, complete conversion with quantitative yield of alane was confirmed by both SSNMR and hydrogen desorption analysis.« less

High temperature metal hydrides as heat storage materials for solar and related applications.

PubMed

Felderhoff, Michael; Bogdanović, Borislav

2009-01-01

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

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

PubMed Central

Felderhoff, Michael; Bogdanović, Borislav

2009-01-01

For the continuous production of electricity with solar heat power plants the storage of heat at a temperature level around 400 °C is essential. High temperature metal hydrides offer high heat storage capacities around this temperature. Based on Mg-compounds, these hydrides are in principle low-cost materials with excellent cycling stability. Relevant properties of these hydrides and their possible applications as heat storage materials are described. PMID:19333448

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

DOE PAGES

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

2017-02-20

The d-spacing evolution of both in-plane and out-of-plane hydrides has been studied using in situ synchrotron radiation X-ray diffraction during thermo-mechanical cycling of cold-worked stress-relieved Zircaloy-4. The structure of the hydride precipitates is such that the δ{111} d-spacing of the planes aligned with the hydride platelet face is greater than the d-spacing of the 111 planes aligned with the platelet edges. Upon heating from room temperature, the δ{111} planes aligned with hydride plate edges exhibit bi-linear thermally-induced expansion. In contrast, the d-spacing of the (111) plane aligned with the hydride plate face initially contracts upon heating. Furthermore, these experimental resultsmore » can be understood in terms of a reversal of stress state associated with precipitating or dissolving hydride platelets within the α-zirconium matrix.« less

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

PubMed

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

2017-04-01

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

The effect of thermal pre-treatment of titanium hydride (TiH2) powder in argon condition

NASA Astrophysics Data System (ADS)

Franciska P., L.; Erryani, Aprilia; Annur, Dhyah; Kartika, Ika

2018-04-01

Titanium hydride (TiH2) powders are used to enhance the foaming process in the formation of a highly porous metallic material with a cellular structure. But, the low temperature of hydrogen release is one of its problems. The present study, different thermal pre-treatment temperatures were employed to investigate the decomposition behavior of TiH2 to retard or delay a hydrogen gas release process during foaming. As a foaming agent, TiH2 was subjected to various heat treatments prior at 450 and 500°C during 2 hours in argon condition. To study the formation mechanism, the thermal behavior of titanium hydride and hydrogen release are investigated by thermogravimetric analysis (TGA) and differential thermal analysis (DTA). The morphology of pre-treated titanium hydride powders were examined using Scanning Electron Microscope (SEM) while unsure mapping and elemental composition of the pre-treated powders processed by Energy Dispersive Spectroscopy (EDS). To study the phase formation was characterized by X-ray diffraction analysis (XRD). In accordance with the results, an increase in pre-treatment temperature of TiH2 to higher degrees are changing the process of releasing hydrogen from titanium hydride powder. DTA/TGA results showed that thermal pre-treatment TiH2 at 450°C, released the hydrogen gas at 560°C in heat treatment when foaming process. Meanwhile, thermal pre-treatment in TiH2 at 500°C, released the hydrogen gas at 670°C when foaming process. There is plenty of direct evidence for the existence of oxide layers that showed by EDS analysis obtained in SEM. As oxygen is a light element and qualitative proof shows that the higher pre-treatment temperature produces more and thicker oxygen layers on the surface of the TiH2 powder particles. It might the thickness of oxide layer are different from different pre-treatment temperatures, which leading to the differences in the decomposition temperature. But from SEM result that oxidation of the powder does not

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

NASA Technical Reports Server (NTRS)

Rojdev, Kristina; Atwell, William

2016-01-01

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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 intomore » 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.« less

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

PubMed

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

2012-01-01

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

Synthesis and structural study of Ti-rich Mg-Ti hydrides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Asano, Kohta; Kim, Hyunjeong; Sakaki, Kouji

2014-02-26

Mg xTi 1-x (x = 0.15, 0.25, 0.35) alloys were synthesized by means of ball milling. Under a hydrogen pressure of 8 MPa at 423 K these Mg–Ti alloys formed a hydride phase with a face centered cubic (FCC) structure. The hydride for x = 0.25 consisted of single Mg 0.25Ti 0.75H 1.62 FCC phase but TiH 2 and MgH 2 phases were also formed in the hydrides for x = 0.15 and 0.35, respectively. X-ray diffraction patterns and the atomic pair distribution function indicated that numbers of stacking faults were introduced. There was no sign of segregation between Mgmore » and Ti in Mg 0.25Ti 0.75H 1.62. Electronic structure of Mg 0.25Ti 0.75H 1.62 was different from those of MgH 2 and TiH 2, which was demonstrated by 1H nuclear magnetic resonance. This strongly suggested that stable Mg–Ti hydride phase was formed in the metal composition of Mg 0.25Ti 0.75 without disproportion into MgH 2 and TiH 2.« less

Effects of outgassing of loader chamber walls on hydriding of thin films for commercial applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Provo, James L., E-mail: jlprovo@verizon.net

2014-07-01

An important aspect of understanding industrial processing is to know the characteristics of the materials used in such processes. A study was performed to determine the effects of hydriding chamber material on the degree of hydriding for the commercial production of thin film hydride targets for various research universities, commercial companies, and government national laboratories. The goal was to increase the degree of hydriding of various thin film hydrides and to study the vacuum environment during air-exposure hydriding. For this purpose, dynamic residual gas analysis during deuterium gas hydride processing was utilized with erbium thin films, employing a special set-upmore » for direct dynamic hydride gas sampling during processing at elevated temperature and full loading gas pressure. Complete process data for (1) a copper–(1.83 wt. %)beryllium wet hydrogen fired passivated (600 °C–1 h) externally heated pipe hydriding chamber are reported. Dynamic residual gas analysis comparisons during hydriding are presented for hydriding chambers made from (2) alumina (99.8 wt. %), (3) copper (with an interior aluminum coating ∼10 k Å thick, and (4) for a stainless-steel air-fired passivated (900 °C–1 h) chamber. Dynamic data with deuterium gas in the chamber at the hydriding temperature (450 °C) showed the presence and growth of water vapor (D{sub 2}O) and related mixed ion species(H{sub 2}O{sup +}, HDO{sup +}, D{sub 2}O{sup +}, and OD{sup +}) from hydrogen isotope exchange reactions during the 1 h process time. Peaks at mass-to-charge ratios (i.e., m/e) of 12(C{sup +}), 16(CD{sub 2}{sup +}), 17(CHD{sub 2}{sup +}), and 18(CD{sub 3}{sup +}, OD{sup +}) increased for approximately the first half hour of a 1 h hydriding process and then approach steady state. Mass-to-charge peaks at 19(HDO{sup +}) and 20(D{sub 2}O{sup +}) continue to increase throughout the process cycle. Using the m/e = 20 (D{sub 2}O{sup +}) peak intensity from

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

2017-08-08

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

Atomic-scale study of stacking faults in Zr hydrides and implications on hydride formation.

PubMed

Besson, Remy; Thuinet, L; Louchez, Marc-Antoine

2018-06-25

We performed atomic-scale ab initio calculations to investigate the stacking fault (SF) properties of the metastable zeta-Zr2H zirconium hydride. The effect of H near the SF was found to entail the existence of negative SF energies, showing that the zeta compound is probably unstable with respect to shearing in the basal plane. The effect of temperature on SFs was investigated by means of free energy calculations in the quasiharmonic approximation. This evidenced unexpectedly large temperature effects, confirming the main conclusions drawn at 0 K, in particular the zeta mechanical instability. The complex behaviour of H atoms during the shear process suggested zeta-hcp --> Zr2H[111]-fcc as a plausible shear path leading to an fcc compound with same composition as zeta. Finally, as shown by an analysis based on microelasticity, this Zr2H[111]-fcc intermediate compound may be relevant for better interpreting the currently intricate issue of hydride habit planes in zirconium. © 2018 IOP Publishing Ltd.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Auer, Henry; Guehne, Robin; Bertmer, Marko

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

Hydride transfer catalysed by Escherichia coli and Bacillus subtilis dihydrofolate reductase: coupled motions and distal mutations.

PubMed

Hammes-Schiffer, Sharon; Watney, James B

2006-08-29

This paper reviews the results from hybrid quantum/classical molecular dynamics simulations of the hydride transfer reaction catalysed by wild-type (WT) and mutant Escherichia coli and WT Bacillus subtilis dihydrofolate reductase (DHFR). Nuclear quantum effects such as zero point energy and hydrogen tunnelling are significant in these reactions and substantially decrease the free energy barrier. The donor-acceptor distance decreases to ca 2.7 A at transition-state configurations to enable the hydride transfer. A network of coupled motions representing conformational changes along the collective reaction coordinate facilitates the hydride transfer reaction by decreasing the donor-acceptor distance and providing a favourable geometric and electrostatic environment. Recent single-molecule experiments confirm that at least some of these thermally averaged equilibrium conformational changes occur on the millisecond time-scale of the hydride transfer. Distal mutations can lead to non-local structural changes and significantly impact the probability of sampling configurations conducive to the hydride transfer, thereby altering the free-energy barrier and the rate of hydride transfer. E. coli and B. subtilis DHFR enzymes, which have similar tertiary structures and hydride transfer rates with 44% sequence identity, exhibit both similarities and differences in the equilibrium motions and conformational changes correlated to hydride transfer, suggesting a balance of conservation and flexibility across species.

Flow injection for the determination of Se(IV) and Se(VI) by hydride generation atomic absorption spectrometry with microwave oven on-line prereduction of Se(VI) to Se(IV)

NASA Astrophysics Data System (ADS)

Burguera, J. L.; Carrero, P.; Burguera, M.; Rondon, C.; Brunetto, M. R.; Gallignani, M.

1996-12-01

An on-line flow injection system has been developed for the selective determination of Se(IV) and Se(VI) in citric fruit juices and geothermal waters by hydride generation atomic absorption spectrometry with microwave-aided heating prereduction of Se(VI) to Se(IV). The samples and the prereductant solutions (4 mol l -1 HCl for Se(IV) and 12 mol l -1 HCl for Se(VI)) which circulated in a closed-flow circuit were injected by means of a time-based injector. This mixture was displaced by a carrier solution of 1% v/v of hydrochloric acid through a PTFE coil located inside the focused microwave oven and mixed downstream with a borohydride solution to generate the hydride. The linear ranges were 0-120 and 0-100 μg l -1 of Se(IV) and Se(VI), respectively. The detection limits were 1.0 μg l -1 for Se(IV) and 1.5 μg l -1 for Se(VI). The precision (about 2.0-2.5% RSD) and recoveries (96-98% for Se(IV) and 94-98% for Se(VI)) were good. Total selenium values were also obtained by electrothermal atomic absorption spectrometry which agreed with the content of both selenium species. The sample throughput was about 50 measurements per hour. The main advantage of the method is that the selective determination of Se(IV) and Se(VI) in citric fruit juices and geothermal waters is performed in a closed system with a minimum sample manipulation, exposure to the environment, minimum sample waste and operator attention.

Method of making alkali metal hydrides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pecharsky, Vitalij K.; Gupta, Shalabh; Pruski, Marek

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

Metal hydride hydrogen compression: Recent advances and future prospects

DOE PAGES

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

2016-03-17

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

Comparison of palladium and zirconium treated graphite tubes for in-atomizer trapping of hydrogen selenide in hydride generation electrothermal atomization atomic absorption spectrometry

NASA Astrophysics Data System (ADS)

Laborda, Francisco; Medrano, Jesús; Cortés, José I.; Mir, José M.; Castillo, Juan R.

1999-02-01

Zirconium treated graphite tubes were investigated and compared with non-treated and palladium coated ones for in situ trapping of selenium hydride generated in a flow injection system. Selenium was effectively trapped on zirconium treated tubes at trapping temperatures of 300-600°C, similar to those observed for palladium, whereas trapping temperatures higher than 600°C had to be used with non-treated tubes. Zirconium treated tubes used in this work showed good stability up to 300 trapping/atomization cycles, with precision better than 5%, characteristic masses of 42 (peak height) and 133 pg (peak area) of selenium were obtained. Sensitivity of zirconium and palladium treatments were similar, but zirconium offered the advantage of a single application per tube. Detection limits were 0.11 (peak height) and 0.23 ng (peak area) for a 1 ml sample volume.

Transition-Metal Hydride Radical Cations.

PubMed

Hu, Yue; Shaw, Anthony P; Estes, Deven P; Norton, Jack R

2016-08-10

Transition-metal hydride radical cations (TMHRCs) are involved in a variety of chemical and biochemical reactions, making a more thorough understanding of their properties essential for explaining observed reactivity and for the eventual development of new applications. Generally, these species may be treated as the ones formed by one-electron oxidation of diamagnetic analogues that are neutral or cationic. Despite the importance of TMHRCs, the generally sensitive nature of these complexes has hindered their development. However, over the last four decades, many more TMHRCs have been synthesized, characterized, isolated, or hypothesized as reaction intermediates. This comprehensive review focuses on experimental studies of TMHRCs reported through the year 2014, with an emphasis on isolated and observed species. The methods used for the generation or synthesis of TMHRCs are surveyed, followed by a discussion about the stability of these complexes. The fundamental properties of TMHRCs, especially those pertaining to the M-H bond, are described, followed by a detailed treatment of decomposition pathways. Finally, reactions involving TMHRCs as intermediates are described.

Determination of hydride affinities of various aldehydes and ketones in acetonitrile.

PubMed

Zhu, Xiao-Qing; Chen, Xi; Mei, Lian-Rui

2011-05-06

The hydride affinities of 21 typical aldehydes and ketones in acetonitrile were determined by using an experimental method, which is valuable for chemists choosing suitable reducing agents to reduce them. The focus of this paper is to introduce a very facile experimental method, which can be used to determine the hydride affinities of various carbonyl compounds in solution.

Homogeneous hydride formation path in α-Zr: Molecular dynamics simulations with the charge-optimized many-body potential

DOE PAGES

Zhang, Yongfeng; Bai, Xian-Ming; Yu, Jianguo; ...

2016-06-01

A formation path for homogeneous γ hydride formation in hcp α-Zr, from solid solution to the ζ and then the γ hydride, was demonstrated using molecular static calculations and molecular dynamic simulations with the charge-optimized many-body (COMB) potential. Hydrogen has limited solubility in α-Zr. Once the solubility limit is exceeded, the stability of solid solution gives way to that of coherent hydride phases such as the ζ hydride by planar precipitation of hydrogen. At finite temperatures, the ζ hydride goes through a partial hcp-fcc transformation via 1/3 <1¯100> slip on the basal plane, and transforms into a mixture of γmore » hydride and α-Zr. In the ζ hydride, slip on the basal plane is favored thermodynamically with negligible barrier, and is therefore feasible at finite temperatures without mechanical loading. The transformation process involves slips of three equivalent shear partials, in contrast to that proposed in the literature where only a single shear partial was involved. The adoption of multiple slip partials minimizes the macroscopic shape change of embedded hydride clusters and the shear strain accumulation in the matrix, and thus reduces the overall barrier needed for homogeneous γ hydride formation. In conclusion, this formation path requires finite temperatures for hydrogen diffusion without mechanical loading. Therefore, it should be effective at the cladding operating conditions.« less

Method for preparing hydride configurations and reactive metal surfaces

DOEpatents

Silver, G.L.

1984-05-18

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

Phase I. Lanthanum-based Start Materials for Hydride Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

The purpose of Phase I of this work is to focus on developing a La-based start material for making nickel-metal (lanthanum)-hydride batteries based on our carbothermic-silicon process. The goal is to develop a protocol for the manufacture of (La 1-xR x)(Ni 1-yM y)(Si z), where R is a rare earth metal and M is a non-rare earth metal, to be utilized as the negative electrode in nickel-metal hydride (NiMH) rechargeable batteries.

Binary-mask generation for diffractive optical elements using microcomputers.

PubMed

O'Shea, D C; Beletic, J W; Poutous, M

1993-05-10

A new technique for generation of binary masks for the fabrication of diffractive optical elements is investigated. This technique, which uses commercially available desktop-publishing hardware and software in conjunction with a standard photoreduction camera, is much faster and less expensive thanhe conventional methods. The short turnaround time and low cost should give researchers a much greater degree of flexibility in the field of binary optics and enable wider application of diffractive-optics technology. Techniques for generating optical elements by using standard software packages that produce PostScript output are described. An evaluation of the dimensional fidelity of the mask reproduction from design to its realization in photoresist is presented.

Conversion and origin of normal and abnormal temperature dependences of kinetic isotope effect in hydride transfer reactions.

PubMed

Zhu, Xiao-Qing; Li, Xiu-Tao; Han, Su-Hui; Mei, Lian-Rui

2012-05-18

The effects of substituents on the temperature dependences of kinetic isotope effect (KIE) for the reactions of the hydride transfer from the substituted 5-methyl-6-phenyl-5,6-dihydrophenanthridine (G-PDH) to thioxanthylium (TX(+)) in acetonitrile were examined, and the results show that the temperature dependences of KIE for the hydride transfer reactions can be converted by adjusting the nature of the substituents in the molecule of the hydride donor. In general, electron-withdrawing groups can make the KIE to have normal temperature dependence, but electron-donating groups can make the KIE to have abnormal temperature dependence. Thermodynamic analysis on the possible pathways of the hydride transfer from G-PDH to TX(+) in acetonitrile suggests that the transfers of the hydride anion in the reactions are all carried out by the concerted one-step mechanism whether the substituent is an electron-withdrawing group or an electron-donating group. But the examination of Hammett-type free energy analysis on the hydride transfer reactions supports that the concerted one-step hydride transfer is not due to an elementary chemical reaction. The experimental values of KIE at different temperatures for the hydride transfer reactions were modeled by using a kinetic equation formed according to a multistage mechanism of the hydride transfer including a returnable charge-transfer complex as the reaction intermediate; the real mechanism of the hydride transfer and the root that why the temperature dependences of KIE can be converted as the nature of the substituents are changed were discovered.

Release of hydrogen from nanoconfined hydrides by application of microwaves

NASA Astrophysics Data System (ADS)

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

2017-06-01

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

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

NASA Technical Reports Server (NTRS)

Zollars, G. F.

1980-01-01

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

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

PubMed

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

2010-04-01

Titanium powder production by the hydride-dehydride method has been developed as a non-expensive process. In this work, commercially pure grade two Ti specimens were hydrogenated. The hydrided material was milled in a planetary mill. The hydrided titanium powder was dehydrided and then sieved to obtain a particle size between 37 and 125 microm in order to compare it with a commercial powder produced by chemical reduction with a particle size lower than 150 microm. 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.

The development of nickel-metal hydride technology for use in aerospace applications

NASA Technical Reports Server (NTRS)

Rampel, Guy; Johnson, Herschel; Dell, Dan; Wu, Tony; Puglisi, Vince

1992-01-01

The nickel metal hydride technology for battery application is relatively immature even though this technology was made widely known by Philips' scientists as long ago as 1970. Recently, because of the international environmental regulatory pressures being placed on cadmium in the workplace and in disposal practices, battery companies have initiated extensive development programs to make this technology a viable commercial operation. These hydrides do not pose a toxilogical threat as does cadmium. Also, they provide a higher energy density and specific energy when compared to the other nickel based battery technologies. For these reasons, the nickel metal hydride electrochemisty is being evaluated as the next power source for varied applications such as laptop computers, cellular telephones, electric vehicles, and satellites. A parallel development effort is under way to look at aerospace applications for nickel metal hydride cells. This effort is focused on life testing of small wound cells of the commercial type to validate design options and development of prismatic design cells for aerospace applications.

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

NASA Technical Reports Server (NTRS)

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.

Hydride compressor

DOEpatents

Powell, James R.; Salzano, Francis J.

1978-01-01

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

Hydrogen storage and evolution catalysed by metal hydride complexes.

PubMed

Fukuzumi, Shunichi; Suenobu, Tomoyoshi

2013-01-07

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

Formation of novel transition metal hydride complexes with ninefold hydrogen coordination

PubMed Central

Takagi, Shigeyuki; Iijima, Yuki; Sato, Toyoto; Saitoh, Hiroyuki; Ikeda, Kazutaka; Otomo, Toshiya; Miwa, Kazutoshi; Ikeshoji, Tamio; Orimo, Shin-ichi

2017-01-01

Ninefold coordination of hydrogen is very rare, and has been observed in two different hydride complexes comprising rhenium and technetium. Herein, based on a theoretical/experimental approach, we present evidence for the formation of ninefold H- coordination hydride complexes of molybdenum ([MoH9]3−), tungsten ([WH9]3−), niobium ([NbH9]4−) and tantalum ([TaH9]4−) in novel complex transition-metal hydrides, Li5MoH11, Li5WH11, Li6NbH11 and Li6TaH11, respectively. All of the synthesized materials are insulated with band gaps of approximately 4 eV, but contain a sufficient amount of hydrogen to cause the H 1s-derived states to reach the Fermi level. Such hydrogen-rich materials might be of interest for high-critical-temperature superconductivity if the gaps close under compression. Furthermore, the hydride complexes exhibit significant rotational motions associated with anharmonic librations at room temperature, which are often discussed in relation to the translational diffusion of cations in alkali-metal dodecahydro-closo-dodecaborates and strongly point to the emergence of a fast lithium conduction even at room temperature. PMID:28287143

Determination of arsenic speciation in sulfidic waters by Ion Chromatography Hydride-Generation Atomic Fluorescence Spectrometry (IC-HG-AFS).

PubMed

Keller, Nicole S; Stefánsson, Andri; Sigfússon, Bergur

2014-10-01

A method for the analysis of arsenic species in aqueous sulfide samples is presented. The method uses an ion chromatography system connected with a Hydride-Generation Atomic Fluorescence Spectrometer (IC-HG-AFS). With this method inorganic As(III) and As(V) species in water samples can be analyzed, including arsenite (HnAs(III)O3(n-3)), thioarsenite (HnAs(III)S3(n-3)), arsenate (HnAs(V)O4(n-3)), monothioarsenate (HnAs(V)SO3(n-3)), dithioarsenate (HnAs(V)S2O2(n-3)), trithioarsenate (HnAs(V)S3O(n-3)) and tetrathioarsenate (HnAs(V)S4(n-3)). The peak identification and retention times were determined based on standard analysis of the various arsenic compounds. The analytical detection limit was ~1-3 µg L(-1) (LOD), depending on the quality of the baseline. This low detection limit makes this method also applicable to discriminate between waters meeting the drinking water standard of max. 10 µg L(-1) As, and waters that do not meet this standard. The new method was successfully applied for on-site determination of arsenic species in natural sulfidic waters, in which seven species were unambiguously identified. Copyright © 2014 Elsevier B.V. All rights reserved.

A renewed search for short-lived 126Sn in the early Solar System: Hydride generation MC-ICPMS for high sensitivity Te isotopic analysis

NASA Astrophysics Data System (ADS)

Brennecka, Gregory A.; Borg, Lars E.; Romaniello, Stephen J.; Souders, Amanda K.; Shollenberger, Quinn R.; Marks, Naomi E.; Wadhwa, Meenakshi

2017-03-01

Although there is limited direct evidence for supernova input into the nascent Solar System, many models suggest it formed by the gravitational collapse of a molecular cloud that was triggered by a nearby supernova. Existing lines of evidence, mostly in the form of short-lived radionuclides present in the early Solar System, are potentially consistent with this hypothesis, but still allow for alternative explanations. Since the natural production of 126Sn is thought to occur only in supernovae and this isotope has a short half-life (126Sn→126Te, t1/2 = 235 ky), the discovery of extant 126Sn would provide unequivocal proof of supernova input to the early Solar System. Previous attempts to quantify the initial abundance of 126Sn by examining Sn-Te systematics in early solids have been hampered by difficulties in precisely measuring Te isotope ratios in these materials. Thus, here we describe a novel technique that uses hydride generation to dramatically increase the ionization efficiency of Te-an approximately 30-fold increase over previous work. This introduction system, when coupled to a MC-ICPMS, enables high-precision Te isotopic analyses on samples with <10 ng of Te. We used this technique to analyze Te from a unique set of calcium-aluminum-rich inclusions (CAIs) that exhibit an exceptionally large range in Sn/Te ratios, facilitating the search for the short-lived isotope 126Sn. This sample set shows no evidence of live 126Sn, implying at most minor input of supernova material during the time at which the CAIs formed. However, based on the petrology of this sample set combined with the higher than expected concentrations of Sn and Te, as well as the lack of nucleosynthetic anomalies in other isotopes of Te suggest that the bulk of the Sn and Te recovered from these particular refractory inclusions is not of primary origin and thus does not represent a primary signature of Sn-Te systematics of the protosolar nebula during condensation of CAIs or their

A renewed search for short-lived 126 Sn in the early Solar System: Hydride generation MC-ICPMS for high sensitivity Te isotopic analysis

DOE PAGES

Brennecka, Gregory A.; Borg, Lars E.; Romaniello, Stephen J.; ...

2017-03-01

Although there is limited direct evidence for supernova input into the nascent Solar System many models suggest it formed by the gravitational collapse of a molecular cloud that was triggered by a nearby supernova. Existing lines of evidence mostly in the form of short lived radionuclidespresent in the early Solar System are potentially consistent with this hypothesis but still allow for alternative explanations. Since the natural production of Sn-126 is thought to occur only in supernovae and this isotope has a short half-life (Sn-126 -> Te-126 t(1/2) = 235 ky) the discovery of extant Sn-126 would provide unequivocal proof ofmore » supernova input to the early Solar System. Previous attempts to quantify the initial abundance of Sn-126 by examining Sn-Te systematics in early solids have been hampered by difficulties in precisely measuring Te isotope ratios in these materials. Thus here we describe a novel technique that uses hydride generation to dramatically increase the ionization efficiency of Te-an approximately 30-fold increase over previous work. This introduction system when coupled to a MC-ICPMS enables highprecision Te isotopic analyses on samples with < 10 ng of Te. We used this technique to analyze Te from a unique set of calcium-aluminum-rich inclusions (CAIs) that exhibit an exceptionally large range in Sn/Te ratios facilitating the search for the short-lived isotope Sn-126. This sample set shows no evidence of live Sn-126 implying at most minor input of supernova material during the time at which the CAIs formed. However based on the petrology of this sample set combined with the higher than expected concentrations of Sn and Te as well as the lack of nucleosynthetic anomalies in other isotopes of Te suggest that the bulk of the Sn and Te recovered from these particular refractory inclusions is not of primary origin and thus does not represent a primary signature of Sn-Te systematics of the protosolar nebula during condensation of CAIs or their

Hydride Microstructure at the Metal-Oxide Interface of Zircaloy-4 from H.B. Robinson Nuclear Reactor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cinbiz, Mahmut N; Edmondson, Philip D; Terrani, Kurt A

2017-01-01

This study investigates the hydride rim microstructure at the metal-oxide interface of Zircaloy-4 cladding segment removed from H.B. Robinson Nuclear Reactor by utilizing high resolution electron microscopy techniques with energy dispersive x-ray spectroscopy at Oak Ridge National Laboratory under the NSUF Rapid Turnout Experiment program. A complex stacking and orientation of hydride platelets has been observed below the sub-oxide layer. Furthermore, radial hydride platelets have been observed. EDS signals of both Fe and Cr has been reduced within hydrides whereas EDS signal of Sn is unaffected.

The applications of a commercial gas/liquid separator coupled with an inductively coupled plasma mass spectrometer

PubMed Central

Hitchen, Peter; Hutton, Robert; Tye, Christopher

1992-01-01

A commercially available hydride generator, with a novel membrane gas-liquid separator, has been coupled to a new ICPMS instrument which itself features many unique design considerations. Little or no optimization of the mass spectrometer or ionization source was required to obtain excellent analytical data; and a variety of matrices have been analysed. The elements As and Se are usually used to demonstrate the effectiveness of a hydride generation system, and these are of particular importance, bearing in mind potential Ar molecular overlaps with isotopes of interest. The flexibility of the hydride generation ICP-MS system is highlighted, with the inclusion of analytical figures of merit for the elements Sn, Sb, Ge and Hg, as well as As and Se. Data obtained by ‘standard’ pneumatic nebulization on the ICP-MS is compared with that obtained with the hydride generator for all of the elements. Improvements of between 50 and 100 times were gained in measurements of three sigma detection limits for all elements in the determinations, including Hg. Measurements were made on several isotopes for particular elements, and the data is included for the purposes of comparison. Stabilities of between 1 and 2.5% were obtained for 0.5 ppb solutions over 10 min measurement periods, all data is presented without using an internal standard. Finally, analytical data from seawater standards, spiked with low levels of As and Se and calibrated against aqueous standards, demonstrate excellent recoveries. This is of particular interest bearing in mind the well-documented molecular interferences from high chloride matrices on As and Se analysis. PMID:18924920

Oxidation kinetics of hydride-bearing uranium metal corrosion products

NASA Astrophysics Data System (ADS)

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

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

ENVIRONMENTAL REACTIVITY OF SOLID STATE HYDRIDE MATERIALS: MODELING AND TESTING FOR AIR AND WATER EXPOSURE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anton, D.; James, C.; Cortes-Concepcion, J.

2010-05-18

To make commercially acceptable condensed phase hydrogen storage systems, it is important to understand quantitatively the risks involved in using these materials. A rigorous set of environmental reactivity tests have been developed based on modified testing procedures codified by the United Nations for the transportation of dangerous goods. Potential hydrogen storage material, 2LiBH4{center_dot}MgH2 and NH3BH3, have been tested using these modified procedures to evaluate the relative risks of these materials coming in contact with the environment in hypothetical accident scenarios. It is apparent that an ignition event will only occur if both a flammable concentration of hydrogen and sufficient thermalmore » energy were available to ignite the hydrogen gas mixture. In order to predict hydride behavior for hypothesized accident scenarios, an idealized finite element model was developed for dispersed hydride from a breached system. Empirical thermodynamic calculations based on precise calorimetric experiments were performed in order to quantify the energy and hydrogen release rates and to quantify the reaction products resulting from water and air exposure. Both thermal and compositional predictions were made with identification of potential ignition event scenarios.« less

Dehydrogenation, disproportionation and transfer hydrogenation reactions of formic acid catalyzed by molybdenum hydride compounds.

PubMed

Neary, Michelle C; Parkin, Gerard

2015-03-01

The cyclopentadienyl molybdenum hydride compounds, Cp R Mo(PMe 3 ) 3- x (CO) x H (Cp R = Cp, Cp*; x = 0, 1, 2 or 3), are catalysts for the dehydrogenation of formic acid, with the most active catalysts having the composition Cp R Mo(PMe 3 ) 2 (CO)H. The mechanism of the catalytic cycle is proposed to involve (i) protonation of the molybdenum hydride complex, (ii) elimination of H 2 and coordination of formate, and (iii) decarboxylation of the formate ligand to regenerate the hydride species. NMR spectroscopy indicates that the nature of the resting state depends on the composition of the catalyst. For example, (i) the resting states for the CpMo(CO) 3 H and CpMo(PMe 3 )(CO) 2 H systems are the hydride complexes themselves, (ii) the resting state for the CpMo(PMe 3 ) 3 H system is the protonated species [CpMo(PMe 3 ) 3 H 2 ] + , and (iii) the resting state for the CpMo(PMe 3 ) 2 (CO)H system is the formate complex, CpMo(PMe 3 ) 2 (CO)(κ 1 -O 2 CH), in the presence of a high concentration of formic acid, but CpMo(PMe 3 ) 2 (CO)H when the concentration of acid is low. While CO 2 and H 2 are the principal products of the catalytic reaction induced by Cp R Mo(PMe 3 ) 3- x (CO) x H, methanol and methyl formate are also observed. The generation of methanol is a consequence of disproportionation of formic acid, while methyl formate is a product of subsequent esterification. The disproportionation of formic acid is a manifestation of a transfer hydrogenation reaction, which may also be applied to the reduction of aldehydes and ketones. Thus, CpMo(CO) 3 H also catalyzes the reduction of a variety of ketones and aldehydes to alcohols by formic acid, via a mechanism that involves ionic hydrogenation.

Pyrophoric behaviour of uranium hydride and uranium powders

NASA Astrophysics Data System (ADS)

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

2010-01-01

Thermal stability and spontaneous ignition conditions of uranium hydride and uranium metal fine powders have been studied and observed in an original and dedicated experimental device placed inside a glove box under flowing pure argon. Pure uranium hydride powder with low amount of oxide (<0.5 wt.%) was obtained by heat treatment at low temperature in flowing Ar/5%H2. Pure uranium powder was obtained by dehydration in flowing pure argon. Those fine powders showed spontaneous ignition at room temperature in air. An in situ CCD-camera displayed ignition associated with powder temperature measurement. Characterization of powders before and after ignition was performed by XRD measurements and SEM observations. Oxidation mechanisms are proposed.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oguchi, Hiroyuki, E-mail: oguchi@nanosys.mech.tohoku.ac.jp; Micro System Integration Center; Isobe, Shigehito

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.

Combined on-board hydride slurry storage and reactor system and process for hydrogen-powered vehicles and devices

DOEpatents

Brooks, Kriston P; Holladay, Jamelyn D; Simmons, Kevin L; Herling, Darrell R

2014-11-18

An on-board hydride storage system and process are described. The system includes a slurry storage system that includes a slurry reactor and a variable concentration slurry. In one preferred configuration, the storage system stores a slurry containing a hydride storage material in a carrier fluid at a first concentration of hydride solids. The slurry reactor receives the slurry containing a second concentration of the hydride storage material and releases hydrogen as a fuel to hydrogen-power devices and vehicles.

Calculated Hydride Donor Abilities of Five-Coordinate Transition Metal Hydrides [HM(diphosphine)2] (+) (M = Ni, Pd, Pt) as a Function of the Bite Angle and Twist Angle of Diphosphine Ligands

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nimlos, Mark R.; Chang, Christopher H.; Curtis, Calvin J.

2008-07-07

Density functional theory (BLYP and B3LYP) and the polarized continuum model (PCM-UA0) for solvation have been used to investigate the effect of bite angle (P-M-P) of diphosphine ligands and the dihedral or twist angle between diphosphine ligands on the hydride donor abilities of Ni, Pd, and Pt [HM(diphosphine)2]+ complexes. It is found that an increased bite angle for a given transition metal atom results in poorer hydride donor abilities. However, hydride donor abilities for these complexes also decrease as the size of the alkyl side groups on the phosphorus atom increase (Et > Me > H) and with the lengthmore » of the metal phosphorus bond (Ni > Pd = Pt). These trends correlate with an increase in the twist angle between the two diphosphine ligands, which increases from 0° for a square-planar configuration to 90° for a tetrahedral geometry. Shorter M-P bonds, larger substituents on the diphosphine ligands, and larger bite angles all result in increased steric interactions between diphosphine ligands and larger dihedral or twist angles between the diphosphine ligands. The twist angle correlates much more strongly with hydride donor abilities than do bite angles alone. As the twist angle increases, the hydride donor ability decreases in a linear fashion. A frontier orbital analysis has been carried out, and it is shown that the hydride donor ability of [HM(diphosphine)2]+ complexes is largely determined by the energy of the lowest unoccupied molecular orbital of the corresponding [M(diphosphine)2]2+ complex. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.« less

Calculated Hydride Donor Abilities of Five-Coordinate Transition Metal Hydrides [HM(diphosphine)2]+ (M = Ni, Pd, Pt) as a Function of the Bite Angle and Twist Angle of Diphosphine Ligands

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nimlos, Mark; Chang, Christopher H.; Curtis, Calvin J.

2008-06-23

Density functional theory (BLYP and B3LYP) and the polarized continuum model (PCM-UA0) for solvation have been used to investigate the effect of bite angle (P-M-P) of diphosphine ligands and the dihedral or twist angle between diphosphine ligands on the hydride donor abilities of Ni, Pd, and Pt [HM(diphosphine)2]+ complexes. It is found that an increased bite angle for a given transition metal atom results in poorer hydride donor abilities. However, hydride donor abilities for these complexes also decrease as the size of the alkyl side groups on the phosphorus atom increase (Et > Me > H) and with the lengthmore » of the metal phosphorus bond (Ni > Pd = Pt). These trends correlate with an increase in the twist angle between the two diphosphine ligands, which increases from 0° for a square-planar configuration to 90° for a tetrahedral geometry. Shorter M-P bonds, larger substituents on the diphosphine ligands, and larger bite angles all result in increased steric interactions between diphosphine ligands and larger dihedral or twist angles between the diphosphine ligands. The twist angle correlates much more strongly with hydride donor abilities than do bite angles alone. As the twist angle increases, the hydride donor ability decreases in a linear fashion. A frontier orbital analysis has been carried out, and it is shown that the hydride donor ability of [HM(diphosphine)2]+ complexes is largely determined by the energy of the lowest unoccupied molecular orbital of the corresponding [M(diphosphine)2]2+ complex. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.« less

Investigation of long term stability in metal hydrides

NASA Technical Reports Server (NTRS)

Marmaro, Roger W.; Lynch, Franklin E.; Chandra, Dhanesh; Lambert, Steve; Sharma, Archana

1991-01-01

It is apparent from the literature and the results of this study that cyclic degradation of AB(5) type metal hydrides varies widely according to the details of how the specimens are cycled. The Rapid Cycle Apparatus (RCA) used produced less degradation in 5000 to 10000 cycles than earlier work with a Slow Cycle Apparatus (SCA) produced in 1500 cycles. Evidence is presented that the 453 K (356 F) Thermal Aging (TA) time spent in the saturated condition causes hydride degradation. But increasing the cooling (saturation) period in the RCA did not greatly increase the rate of degradation. It appears that TA type degradation is secondary at low temperatures to another degradation mechanism. If rapid cycles are less damaging than slow cycles when the saturation time is equal, the rate of hydriding/dehydriding may be an important factor. The peak temperatures in the RCA were about 30 C lower than the SCA. The difference in peak cycle temperatures (125 C in the SCA, 95 C in RCA) cannot explain the differences in degradation. TA type degradation is similar to cyclic degradation in that nickel peaks and line broadening are observed in X ray diffraction patterns after either form of degradation.

Coupled high performance liquid chromatography-microwave digestion-hydride generation-atomic absorption spectrometry for inorganic and organic arsenic speciation in fish tissue.

PubMed

Villa-Lojo, M C; Alonso-Rodríguez, E; López-Mahía, P; Muniategui-Lorenzo, S; Prada-Rodríguez, D

2002-06-10

A high performance liquid chromatography-microwave digestion-hydride generation-atomic absorption spectrometry (HPLC-MW-HG-AAS) coupled method is described for As(III), As(V), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), arsenobetaine (AsB) and arsenocholine (AsC) determination. A Hamilton PRP-X100 anion-exchange column is used for carrying out the arsenic species separation. As mobile phase 17 mM phosphate buffer (pH 6.0) is used for As(III), As(V), MMA and DMA separation, and ultrapure water (pH 6.0) for AsB and AsC separation. Prior to injection into the HPLC system AsB and AsC are isolated from the other arsenic species using a Waters Accell Plus QMA cartridge. A microwave digestion with K(2)S(2)O(8) as oxidizing agent is used for enhancing the efficiency of conversion of AsB and AsC into arsenate. Detection limits achieved were between 0.3 and 1.1 ng for all species. The method was applied to arsenic speciation in fish samples.

On-line preconcentration and speciation of arsenic by flow injection hydride generation atomic absorption spectrophotometry.

PubMed

Narcise, Cristine Ingrid S; Coo, Lilibeth Dlc; Del Mundo, Florian R

2005-12-15

A flow injection-column preconcentration-hydride generation atomic absorption spectrophotometric (FI-column-HGAAS) method was developed for determining mug/l levels of As(III) and As(V) in water samples, with simultaneous preconcentration and speciation. The speciation scheme involved determining As(V) at neutral pH and As(III+V) at pH 12, with As(III) obtained by difference. The enrichment factor (EF) increased with increase in sample loading volume from 2.5 to 10ml, and for preconcentration using the chloride-form anion exchange column, EFs ranged from 5 to 48 for As(V) and 4 to 24 for As(III+V), with corresponding detection limits of 0.03-0.3 and 0.07-0.3mug/l. Linear concentration range (LCR) also varied with sample loading volume, and for a 5-ml sample was 0.3-5 and 0.2-8mug/l for As(V) and As(III+V), respectively. Sample throughput, which decreased with increase in sample volume, was 8-17 samples/h. For the hydroxide-form column, the EFS for 2.5-10ml samples were 3-23 for As(V) and 2-15 for As(III+V), with corresponding detection limits of 0.07-0.4 and 0.1-0.5mug/l. The LCR for a 5-ml sample was 0.3-10mug/l for As(V) and 0.2-20mug/l for As(III+V). Sample throughput was 10-20 samples/h. The developed method has been effectively applied to tap water and mineral water samples, with recoveries ranging from 90 to 102% for 5-ml samples passed through the two columns.

Neutron diffraction studies of a four-coordinated hydride in near square-planar geometry

DOE PAGES

Liao, Jian -Hong; Dhayal, Rajendra Singh; Wang, Xiaoping; ...

2014-10-07

The structure of a nanospheric polyhydrido copper cluster, [Cu 20(H) 11{S 2P(O iPr) 2} 9], was determined by single-crystal neutron diffraction. Cu 20 cluster consists of an elongated triangular orthobicupola constructed from 18 Cu atoms that encapsulate a [Cu 2H 5} 3- ion in the center with an exceptionally short Cu-Cu distance. The eleven hydrides in the cluster display three different coordination modes to the Cu atoms: Six μ 3-hydrides in pyramidal geometry, two μ 4-hydrides in tetrahedral cavity, and three μ 4-hydrides in an unprecedented near square-planar geometry. The neutron data set was collected on a small crystal ofmore » the size 0.20 mm x 0.50 mm x 0.65 mm for seven days using the Spallation Neutron Source TOPAZ single-crystal time-of-flight Laue diffractometer at the Oak Ridge National Laboratory. Furthermore, the final R-factor is 8.64% for 16014 reflections.« less

Hydride generation coupled to microfunnel-assisted headspace liquid-phase microextraction for the determination of arsenic with UV-Vis spectrophotometry.

PubMed

Hashemniaye-Torshizi, Reihaneh; Ashraf, Narges; Arbab-Zavar, Mohammad Hossein

2014-12-01

In this research, a microfunnel-assisted headspace liquid-phase microextraction technique has been used in combination with hydride generation to determine arsenic (As) by UV-Vis spectrophotometry. The method is based on the reduction of As to arsine (AsH3) in acidic media by sodium tetrahydroborate (NaBH4) followed by its subsequent reaction with silver diethyldithiocarbamate (AgDDC) to give an absorbing complex at 510 nm. The complexing reagent (AgDDC) has been dissolved in a 1:1 (by the volume ratio) mixture of chloroform/chlorobenzene microdroplet and exposed to the generated gaseous arsine via a reversed microfunnel in the headspace of the sample solution. Several operating parameters affecting the performance of the method have been examined and optimized. Acetonitrile solvent has been added to the working samples as a sensitivity enhancement agent. Under the optimized operating conditions, the detection limit has been measured to be 0.2 ng mL(-1) (based on 3sb/m criterion, n b = 8), and the calibration curve was linear in the range of 0.5-12 ng mL(-1). The relative standard deviation for eight replicate measurements was 1.9 %. Also, the effects of several potential interferences have been studied. The accuracy of the method was validated through the analysis of JR-1 geological standard reference material. The method has been successfully applied for the determination of arsenic in raw and spiked soft drink and water samples with the recoveries that ranged from 91 to 106 %.

An all-solid-state metal hydride - Sulfur lithium-ion battery

NASA Astrophysics Data System (ADS)

López-Aranguren, Pedro; Berti, Nicola; Dao, Anh Ha; Zhang, Junxian; Cuevas, Fermín; Latroche, Michel; Jordy, Christian

2017-07-01

A metal hydride is used for the first time as anode in a complete all-solid-state battery with sulfur as cathode and LiBH4 as solid electrolyte. The hydride is a nanocomposite made of MgH2 and TiH2 counterparts. The battery exhibits a high reversible capacity of 910 mAh g-1 with discharge plateaus at 1.8 V and 1.4 V. Moreover, the capacity remains to 85% of the initial value over the 25 first charge/discharge cycles.

Fine structure of the K X-ray absorption spectra of titanium in some hydrides, borides, and silicides (in Russian)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vainshtein, �. E.; Zhurakovskii, E. A.

1959-08-01

X-ray spectral analyses confirmed the hypothesis on the metal-like state of hydrogen in tithnium hydrides. Experiments with titunium borides and silicides indicate the special character and degree of the 3d--level participation in the metallic'' bond between the atoms of various complexes. The structure of metalloid elements becomes more complicated with an increase in the specific number of boron and silicon atoms and the bond between the atoms tends to become covalent. (R.V.J.)

Hydrides of intermetallic compounds with a H/M ratio greater than unity obtained at high hydrogen pressures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Semenenko, K.N.; Klyamkin, S.N.

1993-11-01

Novel hydride phases with H/M > 1 based on Zr{sub 2}Pd, Hf{sub 2}Pd, and Hf{sub 2}Cu (structures of the MoSi{sub 2} type) have been synthesized at high H{sub 2} pressures. The X-ray diffraction investigations of the resulting hydrides have been carried out. Some factors determining the maximum hydrogen content in the hydrides of intermetallic compounds are discussed. A model structure of the hydrides obtained is proposed, which assumes the possibility of direct H-H interactions when the interatomic distances are less than 1 {angstrom}.

High-Frequency Fe-H Vibrations in a Bridging Hydride Complex Characterized by NRVS and DFT.

PubMed

Pelmenschikov, Vladimir; Gee, Leland B; Wang, Hongxin; MacLeod, K Cory; McWilliams, Sean F; Skubi, Kazimer L; Cramer, Stephen P; Holland, Patrick L

2018-05-30

High-spin iron species with bridging hydrides have been detected in species trapped during nitrogenase catalysis, but there are few general methods of evaluating Fe-H bonds in high-spin multinuclear iron systems. An 57 Fe nuclear resonance vibrational spectroscopy (NRVS) study on an Fe(μ-H) 2 Fe model complex reveals Fe-H stretching vibrations for bridging hydrides at frequencies greater than 1200 cm -1 . These isotope-sensitive vibrational bands are not evident in infrared (IR) spectra, showing the power of NRVS for identifying hydrides in this high-spin iron system. Complementary density functional theory (DFT) calculations elucidate the normal modes of the rhomboidal iron hydride core. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Non-aqueous phase cold vapor generation and determination of trace cadmium by atomic fluorescence spectrometry.

PubMed

Lei, Zirong; Chen, Luqiong; Hu, Kan; Yang, Shengchun; Wen, Xiaodong

2018-06-05

Cold vapor generation (CVG) of cadmium was firstly accomplished in non-aqueous media by using solid reductant of potassium borohydride (KBH 4 ) as a derivation reagent. The mixture of surfactant Triton X-114 micelle and octanol was innovatively used as the non-aqueous media for the CVG and atomic fluorescence spectrometry (AFS) was used for the elemental determination. The analyte ions were firstly extracted into the non-aqueous media from the bulk aqueous phase of analyte/sample solution via a novelly established ultrasound-assisted rapidly synergistic cloud point extraction (UARS-CPE) process and then directly mixed with the solid redcutant KBH 4 to generate volatile elemental state cadmium in a specially designed reactor, which was then rapidly transported to a commercial atomic fluorescence spectrometer for detection. Under the optimal conditions, the limit of detection (LOD) for cadmium was 0.004 μg L -1 . Compared to conventional hydride generation (HG)-AFS, the efficiency of non-aqueous phase CVG and the analytical performance of the developed system was considerably improved. Copyright © 2018 Elsevier B.V. All rights reserved.

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

USGS Publications Warehouse

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

1994-01-01

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

Exploring hydride-π interactions and their tuning by σ-hole bonds: an ab initio study

NASA Astrophysics Data System (ADS)

Esrafili, Mehdi D.; Asadollahi, Soheila; Mousavian, Parisasadat

2018-01-01

In the present work, ab initio calculations are performed to investigate the geometry, interaction energy and bonding properties of binary complexes formed between metal-hydrides HMX (M = Be, Mg, Zn and X = H, F, CH3) and a series of π-acidic heteroaromatic rings. In all the resulting complexes, the heteroaromatic ring acts as a Lewis acid (electron acceptor), while the H atom of the HMX molecule acts as a Lewis base (electron donor). The nature of this interaction, called 'hydride-π' interaction, is explored in terms of molecular electrostatic potential, non-covalent interaction, quantum theory of atoms in molecules and natural bond orbital analyses. The results show that the interaction energies of these hydride-π interactions are between -1.24 and -2.72 kcal/mol. Furthermore, mutual influence between the hydride-π and halogen- or pnicogen-bonding interactions is studied in complexes in which these interactions coexist. For a given π-acidic ring, the formation of the pnicogen-bonding induces a larger enhancing effect on the strength of hydride-π bond than the halogen-bonding.

METHOD OF PREPARING SINTERED ZIRCONIUM METAL FROM ITS HYDRIDES

DOEpatents

Angier, R.P.

1958-02-11

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

Synthesis of bulk chromium hydrides under pressure of up to 120 GPa

NASA Astrophysics Data System (ADS)

Marizy, Adrien; Geneste, Grégory; Loubeyre, Paul; Guigue, Bastien; Garbarino, Gaston

2018-05-01

Stable compounds in the Cr-H system have been synthesized through a direct reaction of chromium and hydrogen in a laser-heated diamond-anvil cell and investigated using synchrotron x-ray diffraction up to 120 GPa . The sequence of hydrides CrH, Cr2H3 , and CrH2 has been observed by increasing pressure. The known ɛ -h c p -CrH hydride is formed above 3 GPa . A Cr2H3 hydride with a C 2 /m structure appears spontaneously above 19 GPa , as a result of the filling of the tetrahedral sites of ɛ -CrH. YAG laser heating helps dissolve more hydrogen inside the h c p chromium structure to synthesize a CrH2 compound with a P n m a structure from 30 GPa on. The volume expansion per hydrogen atom in octahedral and tetrahedral sites is measured up to the 100-GPa pressure range. The formation pressures and structures of these chromium interstitial hydrides are in very good agreement with DFT calculations. However, despite multiple heating attempts up to 100 GPa , no evidence of the stability of the predicted CrH3 compound could be found.

Validation of a hydride generation atomic absorption spectrometry methodology for determination of mercury in fish designed for application in the Brazilian national residue control plan.

PubMed

Damin, Isabel C F; Santo, Maria A E; Hennigen, Rosmari; Vargas, Denise M

2013-01-01

In the present study, a method for the determination of mercury (Hg) in fish was validated according to ISO/IEC 17025, INMETRO (Brazil), and more recent European recommendations (Commission Decision 2007/333/EC and 2002/657/EC) for implementation in the Brazilian Residue Control Plan (NRCP) in routine applications. The parameters evaluated in the validation were investigated in detail. The results obtained for limit of detection and quantification were respectively, 2.36 and 7.88 μg kg(-1) of Hg. While the recovery varies between 90-96%. The coefficient of variation was of 4.06-8.94% for the repeatability. Furthermore, a comparison using an external proficiency testing scheme was realized. The results of method validated for the determination of the mercury in fish by Hydride generation atomic absorption spectrometry were considered suitable for implementation in routine analysis.

Development of Hydrogen Storage Tank Systems Based on Complex Metal Hydrides

PubMed Central

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

2015-01-01

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

The storage of hydrogen in the form of metal hydrides: An application to thermal engines

NASA Technical Reports Server (NTRS)

Gales, C.; Perroud, P.

1981-01-01

The possibility of using LaNi56, FeTiH2, or MgH2 as metal hydride storage sytems for hydrogen fueled automobile engines is discussed. Magnesium copper and magnesium nickel hydrides studies indicate that they provide more stable storage systems than pure magnesium hydrides. Several test engines employing hydrogen fuel have been developed: a single cylinder motor originally designed for use with air gasoline mixture; a four-cylinder engine modified to run on an air hydrogen mixture; and a gas turbine.

Determination of the heat of hydride formation/decomposition by high-pressure differential scanning calorimetry (HP-DSC).

PubMed

Rongeat, Carine; Llamas-Jansa, Isabel; Doppiu, Stefania; Deledda, Stefano; Borgschulte, Andreas; Schultz, Ludwig; Gutfleisch, Oliver

2007-11-22

Among the thermodynamic properties of novel materials for solid-state hydrogen storage, the heat of formation/decomposition of hydrides is the most important parameter to evaluate the stability of the compound and its temperature and pressure of operation. In this work, the desorption and absorption behaviors of three different classes of hydrides are investigated under different hydrogen pressures using high-pressure differential scanning calorimetry (HP-DSC). The HP-DSC technique is used to estimate the equilibrium pressures as a function of temperature, from which the heat of formation is derived. The relevance of this procedure is demonstrated for (i) magnesium-based compounds (Ni-doped MgH2), (ii) Mg-Co-based ternary hydrides (Mg-CoHx) and (iii) Alanate complex hydrides (Ti-doped NaAlH4). From these results, it can be concluded that HP-DSC is a powerful tool to obtain a good approximation of the thermodynamic properties of hydride compounds by a simple and fast study of desorption and absorption properties under different pressures.

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

PubMed

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

2015-04-02

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

Determination of inorganic arsenic and its organic metabolites in urine by flow-injection hydride generation atomic absorption spectrometry.

PubMed

Hanna, C P; Tyson, J F; McIntosh, S

1993-08-01

A method has been developed for the determination of inorganic arsenic [As(III) and As(V)] and its organic metabolites (monomethylarsenic and dimethylarsenic) in urine by flow-injection hydride generation atomic absorption spectrometry. The nontoxic seafood-derived arsenobetaine and arsenocholine species were first separated by a solid-phase extraction procedure. The remaining sample was digested with a mixture of nitric and sulfuric acids and potassium dichromate, followed by attack with hydrogen peroxide. The resulting As(V) was reduced to As(III) with potassium iodide in hydrochloric acid before injection into the flow-injection manifold. The percentage analytical recoveries (mean +/- 95% confidence interval) of various arsenic species added to a urine specimen at 250 micrograms/L were 108 +/- 2, 112 +/- 11, 104 +/- 7, and 95 +/- 5 for As(III), As(V), monomethylarsenic, and dimethylarsenic, respectively. For the determination of arsenic in Standard Reference Material 2670 (toxic metals in human urine), results agreed with the certified value (480 +/- 100 micrograms/L). Analyses of samples for the Centre de Toxicologie du Quebec, containing seafood-derived species, demonstrated the viability of the separation procedure. Detection limits were between 0.1 and 0.2 microgram/L in the solution injected into the manifold, and precision at 10 micrograms/L was between 2% and 3% (CV). These preliminary results show that the method might be applicable to determinations of arsenic in a range of clinical urine specimens.

A review of catalyst-enhanced magnesium hydride as a hydrogen storage material

NASA Astrophysics Data System (ADS)

Webb, C. J.

2015-09-01

Magnesium hydride remains an attractive hydrogen storage material due to the high hydrogen capacity and low cost of production. A high activation energy and poor kinetics at practical temperatures for the pure material have driven research into different additives to improve the sorption properties. This review details the development of catalytic additives and their effect on the activation energy, kinetics and thermodynamic properties of magnesium hydride.

Complex hydrides for hydrogen storage

DOEpatents

Zidan, Ragaiy

2006-08-22

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

Structure and Thermodynamical Properties of Zirconium Hydrides from First-Principle

NASA Astrophysics Data System (ADS)

Blomqvist, Jakob; Olofsson, Johan; Alvarez, Anna-Maria; Bjerkén, Christina

Zirconium alloys are used as nuclear fuel cladding material due to their mechanical and corrosion resistant properties together with their favorable cross-section for neutron scattering. At running conditions, however, there will be an increase of hydrogen in the vicinity of the cladding surface at the water side of the fuel. The hydrogen will diffuse into the cladding material and at certain conditions, such as lower temperatures and external load, hydrides will precipitate out in the material and cause well known embrittlement, blistering and other unwanted effects. Using phase-field methods it is now possible to model precipitation buildup in metals, for example as a function of hydrogen concentration, temperature and external load, but the technique relies on input of parameters, such as the formation energy of the hydrides and matrix. To that end, we have computed, using the density functional theory (DFT) code GPAW, the latent heat of fusion as well as solved the crystal structure for three zirconium hydride polymorphs: δ-ZrH1.6, γ-ZrH, and Є-ZrH2.

Thermodynamic and Kinetic Properties of Metal Hydrides from First-Principles Calculations

NASA Astrophysics Data System (ADS)

Michel, Kyle Jay

In an effort to minimize the worldwide dependence on fossil fuels, much research has focused on the development of hydrogen fuel cell vehicles. Among the many challenges currently facing the transition to such an alternative energy economy is the storage of hydrogen in an economical and practical way. One class of materials that has presented itself as a possible candidate is solid metal hydrides. These materials chemically bind hydrogen and on heating, release the gas which can then be used to generate power as needed for the vehicle. In order to meet guidelines that have been set for such a storage system, hydrogen must be released rapidly in a narrow temperature range of -40 to 80°C with all reactions being reversible. This sets both thermodynamic and kinetic requirements for the design of candidate metal hydrides. First-principles calculations are well-suited for the task of exploring reactions involving metal hydrides. Here, density-functional theory is used to calculate properties of these materials at the quantum mechanical level of accuracy. In particular, three systems have been investigated: 1. Li-Mg-N-H. Reactions between all known compounds in this system are systematically investigated in order to predict thermodynamically allowed reactions that release hydrogen. The properties of these reactions are compared to the requirements set for hydrogen storage systems. Additionally, ground-state structures are predicted for Li2Mg(NH)2 and Li 4Mg(NH)3. 2. Na-Al-H. The kinetics of mass transport during the (de)hydrogenation of the well-known metal hydride NaAlH4 are investigated. A model is developed to study the flux of native defects through phases involved in these reactions. Since it is also known that titanium is an effective catalyst for both dehydrogenation and rehydrogenation, the effect of Ti substitution in bulk lattices on the kinetics of mass transport is investigated. Results are compared to experiments in order to determine if mass transport

Synthesis of a Silyl Cobalt Hydride and Its Catalytic Performance in Kumada Coupling Reactions.

PubMed

Xu, Shilu; Zhang, Peng; Li, Xiaoyan; Xue, Benjing; Sun, Hongjian; Fuhr, Olaf; Fenske, Dieter

2017-06-01

Four silyl [P,Si]-chelate cobalt complexes (2-5) have been synthesized through the chelate-assisted Si-H activation of bidentate preligand ortho-HSi(Me) 2 (PPh 2 )C 6 H 4 (1) with CoMe(PMe 3 ) 4 and CoCl(PMe 3 ) 3 . The silyl Co I complex, Co(PMe 3 ) 3 (1-Si(Me) 2 -2-(PPh 2 )C 6 H 4 ) (2), was synthesized by Si-H activation of 1 with CoMe(PMe 3 ) 4 or by combining complex 5 with MeLi and PMe 3 . Complex 2 was treated with CH 3 I or EtBr, generating the silyl Co II products CoI(PMe 3 ) 2 (1-Si(Me) 2 -2-(PPh 2 )C 6 H 4 ) (3) and CoBr(PMe 3 ) 2 (1-Si(Me) 2 -2-(PPh 2 )C 6 H 4 ) (4). The silyl Co III hydride, CoHCl(PMe 3 ) 2 (1-Si(Me) 2 -2-(PPh 2 )C 6 H 4 ) (5), was obtained by the reaction of complex 1 with CoCl(PMe 3 ) 3 . The catalytic performance of complex 5 was explored for Kumada coupling reactions, showing good to excellent catalytic efficiency with 2 mol % catalyst loading for the reactions of aryl chlorides or aryl bromides with Grignard reagents. It is noteworthy that the synthesis of 5 as a chelate complex is easier than that of previously reported [PSiP]-pincer cobalt hydride. With similar catalytic efficiency for Kumada reactions, the catalyst loading (2 %) of 5 was lower than that (5 %) of [PSiP]-pincer cobalt hydride. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of electron doping on the stability of the metal hydride NaH

NASA Astrophysics Data System (ADS)

Olea-Amezcua, M. A.; Rivas-Silva, J. F.; de la Peña-Seaman, O.; Heid, R.; Bohnen, K. P.

2017-04-01

Alkali and alkali-earth metal hydrides have high volumetric and gravimetric hydrogen densities, but due to their high thermodynamic stability, they possess high dehydrogenation temperatures which may be reduced by transforming these compounds into less stable states/configurations. We present a systematic computational study of the electron doping effects on the stability of the alkali metal hydride NaH substituted with Mg, using the self-consistent version of the virtual crystal approximation to model the alloy Na1-x Mg x H. The phonon dispersions were studied paying special attention to the crystal stability and the correlations with the electronic structure taking into account the zero point energy contribution. We found that substitution of Na by Mg in the hydride invokes a reduction of the frequencies, leading to dynamical instabilities for Mg content of 25%. The microscopic origin of these instabilities could be related to the formation of ellipsoidal Fermi surfaces centered at the L point due to the metallization of the hydride by the Mg substitution. Applying the quasiharmonic approximation, thermodynamic properties like heat capacities, vibrational entropies and vibrational free energies as a function of temperature at zero pressure are obtained. These properties determine an upper temperature for the thermodynamic stability of the hydride, which decreases from 600 K for NaH to 300 K at 20% Mg concentration. This significant reduction of the stability range indicates that dehydrogenation could be favoured by electron doping of NaH.

Formation of superconducting platinum hydride under pressure: an ab initio approach

NASA Astrophysics Data System (ADS)

Kim, Duck Young; Scheicher, Ralph; Pickard, Chris; Needs, Richard; Ahuja, Rajeev

2012-02-01

Noble metals such as Pt, Au, or Re are commonly used for electrodes and gaskets in diamond anvil cells for high-pressure research because they are expected to rarely undergo structural transformation and possess simple equation of states. Specifically Pt has been used widely for high-pressure experiments and has been considered to resist hydride formation under pressure. Pressure-induced reactions of metals with hydrogen are in fact quite likely because hydrogen atoms can occupy interstitial positions in the metal lattice, which can lead to unexpected effects in experiments. In our study, PRL 107 117002 (2011), we investigated crystal structures using ab initio random structure searching (AIRSS) and predicted the formation of platinum mono-hydride above 22 GPa and superconductivity Tc was estimated to be 10 -- 25 K above around 80 GPa. Furthermore, we showed that the formation of fcc noble metal hydrides under pressure is common and examined the possibility of superconductivity in these materials.

Metal hydride reasearch and development program at Brookhaven National Laboratory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, J.R.; Reilly, J.J.

1978-01-01

A progress report is presented covering work performed in the hydrogen materials development program at Brookhaven National Laboratory (BNL) for FY78 which encompasses the time period from October 1, 1977 through September 30, 1978. The subjects to be discussed here concern properties of importance in the utilization of metal hydrides as energy storage media. Most of the areas of research were initiated prior to FY78, however all of the results contained in this manuscript were obtained during the aforementioned period of time. The following subjects will be discussed: the properties of ferro-titanium and chrome-titanium alloy hydrides.

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

PubMed

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

2018-02-01

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

Calculations of hydrogen diffusivity in Zr-based alloys: Influence of alloying elements and effect of stress

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, J.; Jiang, C.; Zhang, Y.

This report summarizes the progress on modeling hydrogen diffusivity in Zr-based alloys. The presence of hydrogen (H) can detrimentally affect the mechanical properties of many metals and alloys. To mitigate these detrimental effects requires fundamental understanding of the thermodynamics and kinetics governing H pickup and hydride formation. In this work, we focus on H diffusion in Zr-based alloys by studying the effects of alloying elements and stress, factors that have been shown to strongly affect H pickup and hydride formation in nuclear fuel claddings. A recently developed accelerated kinetic Monte Carlo method is used for the study. It is foundmore » that for the alloys considered here, H diffusivity depends weakly on composition, with negligible effect at high temperatures in the range of 600-1200 K. Therefore, the small variation in compositions of these alloys is likely not a major cause of the very different H pickup rates. In contrast, stress strongly affects H diffusivity. This effect needs to be considered for studying hydride formation and delayed hydride cracking.« less

An evaluation of the bioaccessibility of arsenic in corn and rice samples based on cloud point extraction and hydride generation coupled to atomic fluorescence spectrometry.

PubMed

Castor, José Martín Rosas; Portugal, Lindomar; Ferrer, Laura; Hinojosa-Reyes, Laura; Guzmán-Mar, Jorge Luis; Hernández-Ramírez, Aracely; Cerdà, Víctor

2016-08-01

A simple, inexpensive and rapid method was proposed for the determination of bioaccessible arsenic in corn and rice samples using an in vitro bioaccessibility assay. The method was based on the preconcentration of arsenic by cloud point extraction (CPE) using o,o-diethyldithiophosphate (DDTP) complex, which was generated from an in vitro extract using polyethylene glycol tert-octylphenyl ether (Triton X-114) as a surfactant prior to its detection by atomic fluorescence spectrometry with a hydride generation system (HG-AFS). The CPE method was optimized by a multivariate approach (two-level full factorial and Doehlert designs). A photo-oxidation step of the organic species prior to HG-AFS detection was included for the accurate quantification of the total As. The limit of detection was 1.34μgkg(-1) and 1.90μgkg(-1) for rice and corn samples, respectively. The accuracy of the method was confirmed by analyzing certified reference material ERM BC-211 (rice powder). The corn and rice samples that were analyzed showed a high bioaccessible arsenic content (72-88% and 54-96%, respectively), indicating a potential human health risk. Copyright © 2016 Elsevier Ltd. All rights reserved.

A Twist on Facial Selectivity of Hydride Reductions of Cyclic Ketones: Twist-Boat Conformers in Cyclohexanone, Piperidone, and Tropinone Reactions

PubMed Central

2015-01-01

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). PMID:25372509

Materials for Hydrogen Storage: From Nanostructures to Complex Hydrides

NASA Astrophysics Data System (ADS)

Jena, Puru

2006-03-01

The limited supply of fossil fuels, its adverse effect on the environment, and growing worldwide demand for energy has necessitated the search for new and clean sources of energy. The possibility of using hydrogen to meet this growing energy need has rekindled interest in the study of safe, efficient, and economical storage of hydrogen. This talk will discuss the issues and challenges in storing hydrogen in light complex hydrides and discuss the role of nanostructuring and catalysts that can improve the thermodynamics and kinetics of hydrogen. In particular, we will discuss how studies of clusters can help elucidate the fundamental mechanisms for hydrogen storage and how these can be applied in Boron Nitride and Carbon nanocages and how metallization of these nanostructures is necessary to store hydrogen with large gravimetric density. We will also discuss the properties of complex light metal hydrides such as alanates and magnesium hydrides that can store up to 18 wt % hydrogen, although the temperature where hydrogen desorbs is rather high. Using first principles calculations, we will provide a fundamental understanding of the electronic structure and stability of these systems and how it is affected due to catalysts. It is hoped that the understanding gained here can be useful in designing better catalysts as well as hosts for hydrogen storage.

Hydrogen storage material and process using graphite additive with metal-doped complex hydrides

DOEpatents

Zidan, Ragaiy [Aiken, SC; Ritter, James A [Lexington, SC; Ebner, Armin D [Lexington, SC; Wang, Jun [Columbia, SC; Holland, Charles E [Cayce, SC

2008-06-10

A hydrogen storage material having improved hydrogen absorbtion and desorption kinetics is provided by adding graphite to a complex hydride such as a metal-doped alanate, i.e., NaAlH.sub.4. The incorporation of graphite into the complex hydride significantly enhances the rate of hydrogen absorbtion and desorption and lowers the desorption temperature needed to release stored hydrogen.

Complex transition metal hydrides: linear correlation of countercation electronegativity versus T-D bond lengths.

PubMed

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

2015-06-30

For homoleptic 18-electron complex hydrides, an inverse linear correlation has been established between the T-deuterium bond length (T = Fe, Co, Ni) and the average electronegativity of the metal countercations. This relationship can be further employed towards aiding structural solutions and predicting physical properties of novel complex transition metal hydrides.

Determination of inorganic arsenic in algae using bromine halogenation and on-line nonpolar solid phase extraction followed by hydride generation atomic flourescence spectrometry

USDA-ARS?s Scientific Manuscript database

Accurate, stable and fast analysis of toxic inorganic arsenic (iAs) in complicated and arsenosugar-rich algae matrix is always a challenge. Herein, a novel analytical method for iAs in algae was reported, using bromine halogenation and on-line nonpolar solid phase extraction (SPE) followed by hydrid...

Elemental analysis using temporal gating of a pulsed neutron generator

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mitra, Sudeep

Technologies related to determining elemental composition of a sample that comprises fissile material are described herein. In a general embodiment, a pulsed neutron generator periodically emits bursts of neutrons, and is synchronized with an analyzer circuit. The bursts of neutrons are used to interrogate the sample, and the sample outputs gamma rays based upon the neutrons impacting the sample. A detector outputs pulses based upon the gamma rays impinging upon the material of the detector, and the analyzer circuit assigns the pulses to temporally-based bins based upon the analyzer circuit being synchronized with the pulsed neutron generator. A computing devicemore » outputs data that is indicative of elemental composition of the sample based upon the binned pulses.« less

Hydride Transfer in DHFR by Transition Path Sampling, Kinetic Isotope Effects, and Heavy Enzyme Studies

PubMed Central

Wang, Zhen; Antoniou, Dimitri; Schwartz, Steven D.; Schramm, Vern L.

2016-01-01

Escherichia coli dihydrofolate reductase (ecDHFR) is used to study fundamental principles of enzyme catalysis. It remains controversial whether fast protein motions are coupled to the hydride transfer catalyzed by ecDHFR. Previous studies with heavy ecDHFR proteins labeled with 13C, 15N, and nonexchangeable 2H reported enzyme mass-dependent hydride transfer kinetics for ecDHFR. Here, we report refined experimental and computational studies to establish that hydride transfer is independent of protein mass. Instead, we found the rate constant for substrate dissociation to be faster for heavy DHFR. Previously reported kinetic differences between light and heavy DHFRs likely arise from kinetic steps other than the chemical step. This study confirms that fast (femtosecond to picosecond) protein motions in ecDHFR are not coupled to hydride transfer and provides an integrative computational and experimental approach to resolve fast dynamics coupled to chemical steps in enzyme catalysis. PMID:26652185

Hydrogen Storage in Metal Hydrides

DTIC Science & Technology

1990-08-01

TitlePage 1. Properties of Reticulated Carbon Foam 26 2. Hydrogen Storage Capacity of Various Metal Hydrides 27 iv INTRODUCTION This is the final technical...pores, and results in coating of only the surface. The substrate for the fabrication of the magnesium foam was a reticulated carbon foam. This...material is an open-pore foam composed solely of vitreous carbon . It has an exceptionally high void volume (97%) and a high surface area, combined with self

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

NASA Astrophysics Data System (ADS)

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

2017-03-01

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

ESCHER: An interactive mesh-generating editor for preparing finite-element input

NASA Technical Reports Server (NTRS)

Oakes, W. R., Jr.

1984-01-01

ESCHER is an interactive mesh generation and editing program designed to help the user create a finite-element mesh, create additional input for finite-element analysis, including initial conditions, boundary conditions, and slidelines, and generate a NEUTRAL FILE that can be postprocessed for input into several finite-element codes, including ADINA, ADINAT, DYNA, NIKE, TSAAS, and ABUQUS. Two important ESCHER capabilities, interactive geometry creation and mesh archival storge are described in detail. Also described is the interactive command language and the use of interactive graphics. The archival storage and restart file is a modular, entity-based mesh data file. Modules of this file correspond to separate editing modes in the mesh editor, with data definition syntax preserved between the interactive commands and the archival storage file. Because ESCHER was expected to be highly interactive, extensive user documentation was provided in the form of an interactive HELP package.

Multielemental Determination of As, Bi, Ge, Sb, and Sn in Agricultural Samples Using Hydride Generation Coupled to Microwave-Induced Plasma Optical Emission Spectrometry.

PubMed

Machado, Raquel C; Amaral, Clarice D B; Nóbrega, Joaquim A; Araujo Nogueira, Ana Rita

2017-06-14

A microwave-induced plasma optical emission spectrometer with N 2 -based plasma was combined with a multimode sample introduction system (MSIS) for hydride generation (HG) and multielemental determination of As, Bi, Ge, Sb, and Sn in samples of forage, bovine liver, powdered milk, agricultural gypsum, rice, and mineral fertilizer, using a single condition of prereduction and reduction. The accuracy of the developed analytical method was evaluated using certified reference materials of water and mineral fertilizer, and recoveries ranged from 95 to 106%. Addition and recovery experiments were carried out, and the recoveries varied from 85 to 117% for all samples evaluated. The limits of detection for As, Bi, Ge, Sb, and Sn were 0.46, 0.09, 0.19, 0.46, and 5.2 μg/L, respectively, for liquid samples, and 0.18, 0.04, 0.08, 0.19, and 2.1 mg/kg, respectively, for solid samples. The method proposed offers a simple, fast, multielemental, and robust alternative for successful determination of all five analytes in agricultural samples with low operational cost without compromising analytical performance.

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

PubMed

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

2016-03-11

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.

The Planck Sorption Cooler: Using Metal Hydrides to Produce 20 K

NASA Technical Reports Server (NTRS)

Pearson, David P.; Bowman, R.; Prina, M.; Wilson, P.

2006-01-01

The Jet Propulsion Laboratory has built and delivered two continuous closed cycle hydrogen Joule-Thomson (JT) cryocoolers for the ESA Planck mission, which will measure the anisotropy in the cosmic microwave background. The metal hydride compressor consists of six sorbent beds containing LaNi4.78Sn0.22 alloy and a low pressure storage bed of the same material. Each sorbent bed contains a separate gas-gap heat switch that couples or isolates the bed with radiators during the compressor operating cycle. ZrNiHx hydride is used in this heat switch. The Planck compressor produces hydrogen gas at a pressure of 48 Bar by heating the hydride to approx.450 K. This gas passes through a cryogenic cold end consisting of a tube-in-tube heat exchanger, three pre-cooling stages to bring the gas to nominally 52 K, a JT value to expand the gas into the two-phase regime at approx.20 K, and two liquid - vapor heat exchangers that must remove 190 and 646 mW of heat respectively.

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

ERIC Educational Resources Information Center

Rioux, Frank; Harriss, Donald K.

1980-01-01

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

Wind energy harvesting using a piezo-composite generating element (PCGE)

NASA Astrophysics Data System (ADS)

Tien, Cam Minh Tri; Goo, Nam-Seo

2010-04-01

Energy can be reclaimed and stored for later use to recharge a battery or power a device through a process called energy harvesting. Piezoelectric is being widely investigated for use in harvesting surrounding energy sources such as sun, wind, tides, indoor lighting, body movement or machine vibration, etc. This paper introduces a wind energy harvesting device using a Piezo-Composite Generating Element (PCGE). The PCGE is composed of layers of carbon/epoxy, PZT ceramic, and glass/epoxy cured at an elevated temperature. In the prototype, The PCGE performs as a secondary beam element. One end of the PCGE is attached on the frame of the device. The fan blade rotates in the direction of the wind and hits the PCGE's tip. When the PCGE is excited, the effects of the beam deformation allow it to generate electric power. In wind tunnel experiments, the PCGE is excited to vibrate at its first natural frequency and generates the power up to 8.5 mW. The prototype can harvest energy in urban regions with minor wind movement.

Optical properties of metal-hydride switchable films

NASA Astrophysics Data System (ADS)

Griessen, Ronald

2001-03-01

In 1996 we discovered that yttrium-, lanthanum-, and rare-earth-hydride (REHx) films [1] protected by a thin palladium layer, exhibit spectacular changes in their optical properties when the hydrogen concentration x is increased from 2 to 3. For example, a 500 nm thick YH2 film is metallic and shiny while YH3 is yellowish and transparent. The transition is reversible, fast [2, 3], and can simply be induced by adding or removing hydrogen from the gas phase, an electrolyte or from an H containing liquid. The optical switching that occurs near the metal-insulator transition of these hydrides is remarkably robust as it is not affected by structural or compositional disorder. It occurs in polycrystalline and epitaxial films, in alloys with cubic or hexagonal crystal structures,and deuterides [4] switch as well as hydrides. At small length scales epitaxial YHx films exhibit surprising structural properties which open the way to pixel-by-pixel optical switching [5]. Colour-neutral switchable mirrors based on RE-Mg alloys [6] can be used in all-solid-state switchable devices. Newest results for Rare-Earth free switchable mirrors will be presented. [1] J. N. Huiberts, R. Griessen, J. H. Rector, R. J. Wijngaarden, J. P. Dekker, D. G. de Groot and N. J. Koeman, Nature 380 (1996) 231; [2] S. J. van der Molen, J. W. J. Kerssemakers, J. H. Rector, N. J. Koeman, B. Dam, R. Griessen, J. Appl. Phys. 86 (1999) 6107; [3] F. J. A. den Broeder, S. J. van der Molen, et al., Nature 394 (1998)656; [4] A. T. M. van Gogh, E. S. Kooij, R. Griessen, Phys. Rev. Lett. 83 (1999) 4614; [5] J. W. J. Kerssemakers, S. J. van der Molen and R. Griessen, Nature 406 (2000) 489; [6] P. van der Sluis, M. Ouwerkerk and P. A. Duine, Appl. Phys. Lett. 70 (1997) 3356.

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

NASA Technical Reports Server (NTRS)

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

1994-01-01

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

Hydride-Meisenheimer Complex Formation and Protonation as Key Reactions of 2,4,6-Trinitrophenol Biodegradation by Rhodococcus erythropolis

PubMed Central

Rieger, Paul-Gerhard; Sinnwell, Volker; Preuß, Andrea; Francke, Wittko; Knackmuss, Hans-Joachim

1999-01-01

Biodegradation of 2,4,6-trinitrophenol (picric acid) by Rhodococcus erythropolis HLPM-1 proceeds via initial hydrogenation of the aromatic ring system. Here we present evidence for the formation of a hydride-Meisenheimer complex (anionic ς-complex) of picric acid and its protonated form under physiological conditions. These complexes are key intermediates of denitration and productive microbial degradation of picric acid. For comparative spectroscopic identification of the hydride complex, it was necessary to synthesize this complex for the first time. Spectroscopic data revealed the initial addition of a hydride ion at position 3 of picric acid. This hydride complex readily picks up a proton at position 2, thus forming a reactive species for the elimination of nitrite. Cell extracts of R. erythropolis HLPM-1 transform the chemically synthesized hydride complex into 2,4-dinitrophenol. Picric acid is used as the sole carbon, nitrogen, and energy source by R. erythropolis HLPM-1. PMID:9973345

The role of atomic fluorescence spectrometry in the automatic environmental monitoring of trace element analysis

PubMed Central

Stockwell, P. B.; Corns, W. T.

1993-01-01

Considerable attention has been drawn to the environmental levels of mercury, arsenic, selenium and antimony in the last decade. Legislative and environmental pressure has forced levels to be lowered and this has created an additional burden for analytical chemists. Not only does an analysis have to reach lower detection levels, but it also has to be seen to be correct. Atomic fluorescence detection, especially when coupled to vapour generation techniques, offers both sensitivity and specificity. Developments in the design of specified atomic fluorescence detectors for mercury, for the hydride-forming elements and also for cadmium, are described in this paper. Each of these systems is capable of analysing samples in the part per trillion (ppt) range reliably and economically. Several analytical applications are described. PMID:18924964

Digitizing for Computer-Aided Finite Element Model Generation.

DTIC Science & Technology

1979-10-10

this approach is a collection of programs developed over the last eight years at the University of Arizona, and called the GIFTS system. This paper...briefly describes the latest version of the system, GIFTS -5, and demonstrates its suitability in a design environment by simple examples. The programs...constituting the GIFTS system were used as a tool for research in many areas, including mesh generation, finite element data base design, interactive

APPLICATION OF SAMPLE PRE-OXIDATION OF ARSENITE IN HUMAN URINE PRIOR TO SPECIATON VIA ON-LINE PHOTO-OXIDATION WITH MEMBRANE HYDRIDE GENRATION AND ICP-MS DETECTION

EPA Science Inventory

A pre-oxidation procedure which converts arsenite (AS(III)) to arsenate (As(VVV)) was investigated in urinary arsenic speciation prior to on-line photo-oxidation hydride-generation with ICP-MS detection. This sample pre-oxidation method eliminates As(III) and As(V) preservation c...

Effect of delivery condition on desorption rate of ZrCo metal hydride bed for fusion fuel cycle

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kang, H.G.; Yun, S.H.; Chung, D.

2015-03-15

For the safety of fusion fuel cycle, hydrogen isotope gases including tritium are stored as metal hydride form. To satisfy fueling requirement of fusion machine, rapid delivery from metal hydride bed is one of major factors for the development of tritium storage and delivery system. Desorption from metal hydride depends on the operation scenario by pressure and temperature control of the bed. The effect of operation scenario and pump performance on desorption rate of metal hydride bed was experimentally investigated using ZrCo bed. The results showed that the condition of pre-heating scenario before actual delivery of gas affected the deliverymore » performance. Different pumps were connected to desorption line from bed and the effect of pump capacity on desorption rate were also found to be significant. (authors)« less

Zirconium hydride containing explosive composition

DOEpatents

Walker, Franklin E.; Wasley, Richard J.

1981-01-01

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

Identification of a catalytic iron-hydride at the H-cluster of [FeFe]-hydrogenase

DOE PAGES

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

2016-12-14

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

Hydride affinities of cumulated, isolated, and conjugated dienes in acetonitrile.

PubMed

Zhu, Xiao-Qing; Liang, Hao; Zhu, Yan; Cheng, Jin-Pei

2008-11-07

The hydride affinities (defined as the enthalpy changes in this work) of 15 polarized dienes [five phenyl sulfone substituted allenes (1a), the corresponding five isolated dienes (1b), and the corresponding five conjugated dienes (1c)] in acetonitrile solution were determined by titration calorimetry for the first time. The results display that the hydride affinity scales of the 15 dienes in acetonitrile range from -71.6 to -73.9 kcal/mol for 1a, from -46.2 to -49.7 kcal/mol for 1b, and from -45.0 to -46.5 kcal/mol for 1c, which indicates that the hydride-obtaining abilities of the cumulated dienes (1a) are not only much larger than those of the corresponding conjugated dienes (1c) but also much larger than those of the corresponding isolated dienes (1b). The hydrogen affinities of the 15 dienes as well as the hydrogen affinities and the proton affinities of the radical anions of the dienes (1(-*)) in acetonitrile were also evaluated by using relative thermodynamic cycles according to Hess's law. The results show that (i) the hydrogen affinities of the neutral dienes 1 cover a range from -44.5 to -45.6 kcal/mol for 1a, from -20.4 to -21.4 kcal/mol for 1b, and from -17.3 to -18.5 kcal/mol for 1c; (ii) the hydrogen affinities of the radical anions of the dienes (1(-*)) in acetonitrile cover a range from -40.6 to -47.2 kcal/mol for 1a(-*), from -21.6 to -29.6 kcal/mol for 1b(-*), and from -10.0 to -15.4 kcal/mol for 1c(-*); (iii) the proton affinities of the 15 1a(-*) in acetonitrile cover a range from -97.0 to -100.6 kcal/mol for 1a(-*), from -77.8 to -83.4 kcal/mol for 1b(-*), and from -66.2 to -68.9 kcal/mol for 1c(-*). The main reasons for the great difference between the cumulated dienes and the corresponding isolated and conjugated dienes in the hydride affinity, hydrogen affinity, and proton affinity have been examined. It is evident that these experimental results should be quite valuable to facilitate the elucidation of the origins of the especially high

A low tritium hydride bed inventory estimation technique

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klein, J.E.; Shanahan, K.L.; Baker, R.A.

2015-03-15

Low tritium hydride beds were developed and deployed into tritium service in Savannah River Site. Process beds to be used for low concentration tritium gas were not fitted with instrumentation to perform the steady-state, flowing gas calorimetric inventory measurement method. Low tritium beds contain less than the detection limit of the IBA (In-Bed Accountability) technique used for tritium inventory. This paper describes two techniques for estimating tritium content and uncertainty for low tritium content beds to be used in the facility's physical inventory (PI). PI are performed periodically to assess the quantity of nuclear material used in a facility. Themore » first approach (Mid-point approximation method - MPA) assumes the bed is half-full and uses a gas composition measurement to estimate the tritium inventory and uncertainty. The second approach utilizes the bed's hydride material pressure-composition-temperature (PCT) properties and a gas composition measurement to reduce the uncertainty in the calculated bed inventory.« less

Thermal enhancement cartridge heater modified (TECH Mod) tritium hydride bed development, Part 1 - Design and fabrication

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klein, J.E.; Estochen, E.G.

The Savannah River Site (SRS) tritium facilities have used first generation (Gen1) LaNi{sub 4.25}Al{sub 0.75} (LANA0.75) metal hydride storage beds for tritium absorption, storage, and desorption. The Gen1 design utilizes hot and cold nitrogen supplies to thermally cycle these beds. Second and third generation (Gen2 and Gen3) storage bed designs include heat conducting foam and divider plates to spatially fix the hydride within the bed. For thermal cycling, the Gen2 and Gen3 beds utilize internal electric heaters and glovebox atmosphere flow over the bed inside the bed external jacket for cooling. The currently installed Gen1 beds require replacement due tomore » tritium aging effects on the LANA0.75 material, and cannot be replaced with Gen2 or Gen3 beds due to different designs of these beds. At the end of service life, Gen1 bed desorption efficiencies are limited by the upper temperature of hot nitrogen supply. To increase end-of-life desorption efficiency, the Gen1 bed design was modified, and a Thermal Enhancement Cartridge Heater Modified (TECH Mod) bed was developed. Internal electric cartridge heaters in the new design to improve end-of-life desorption, and also permit in-bed tritium accountability (IBA) calibration measurements to be made without the use of process tritium. Additional enhancements implemented into the TECH Mod design are also discussed. (authors)« less

THERMAL ENHANCEMENT CARTRIDGE HEATER MODIFIED TECH MOD TRITIUM HYDRIDE BED DEVELOPMENT PART I DESIGN AND FABRICATION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klein, J.; Estochen, E.

The Savannah River Site (SRS) tritium facilities have used 1{sup st} generation (Gen1) LaNi{sub 4.25}Al{sub 0.75} (LANA0.75) metal hydride storage beds for tritium absorption, storage, and desorption. The Gen1 design utilizes hot and cold nitrogen supplies to thermally cycle these beds. Second and 3{sup rd} generation (Gen2 and Gen3) storage bed designs include heat conducting foam and divider plates to spatially fix the hydride within the bed. For thermal cycling, the Gen2 and Gen 3 beds utilize internal electric heaters and glovebox atmosphere flow over the bed inside the bed external jacket for cooling. The currently installed Gen1 beds requiremore » replacement due to tritium aging effects on the LANA0.75 material, and cannot be replaced with Gen2 or Gen3 beds due to different designs of these beds. At the end of service life, Gen1 bed desorption efficiencies are limited by the upper temperature of hot nitrogen supply. To increase end-of-life desorption efficiency, the Gen1 bed design was modified, and a Thermal Enhancement Cartridge Heater Modified (TECH Mod) bed was developed. Internal electric cartridge heaters in the new design to improve end-of-life desorption, and also permit in-bed tritium accountability (IBA) calibration measurements to be made without the use of process tritium. Additional enhancements implemented into the TECH Mod design are also discussed.« less

Key hydride vibrational modes in [NiFe] hydrogenase model compounds studied by resonance Raman spectroscopy and density functional calculations.

PubMed

Shafaat, Hannah S; Weber, Katharina; Petrenko, Taras; Neese, Frank; Lubitz, Wolfgang

2012-11-05

Hydrogenase proteins catalyze the reversible conversion of molecular hydrogen to protons and electrons. While many enzymatic states of the [NiFe] hydrogenase have been studied extensively, there are multiple catalytically relevant EPR-silent states that remain poorly characterized. Analysis of model compounds using new spectroscopic techniques can provide a framework for the study of these elusive states within the protein. We obtained optical absorption and resonance Raman (RR) spectra of (dppe)Ni(μ-pdt)Fe(CO)(3) and [(dppe)Ni(μ-pdt)(μ-H)Fe(CO)(3)][BF(4)], which are structural and functional model compounds for the EPR-silent Ni-SI and Ni-R states of the [NiFe] hydrogenase active site. The studies presented here use RR spectroscopy to probe vibrational modes of the active site, including metal-hydride stretching vibrations along with bridging ligand-metal and Fe-CO bending vibrations, with isotopic substitution used to identify key metal-hydride modes. The metal-hydride vibrations are essentially uncoupled and represent isolated, localized stretching modes; the iron-hydride vibration occurs at 1530 cm(-1), while the nickel-hydride vibration is observed at 945 cm(-1). The significant discrepancy between the metal-hydride vibrational frequencies reflects the slight asymmetry in the metal-hydride bond lengths. Additionally, time-dependent density functional theory (TD-DFT) calculations were carried out to obtain theoretical RR spectra of these compounds. On the basis of the detailed comparison of theory and experiment, the dominant electronic transitions and significant normal modes probed in the RR experiments were assigned; the primary transitions in the visible wavelengths represent metal-to-metal and metal-to-ligand charge transfer bands. Inherent properties of metal-hydride vibrational modes in resonance Raman spectra and DFT calculations are discussed together with the prospects of observing such vibrational modes in metal-hydride-containing proteins. Such a

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

PubMed

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.

Calcium hydride synthesis of Ti-Nb-based alloy powders

NASA Astrophysics Data System (ADS)

Kasimtsev, A. V.; Shuitsev, A. V.; Yudin, S. N.; Levinskii, Yu. V.; Sviridova, T. A.; Alpatov, A. V.; Novosvetlova, E. E.

2017-09-01

The metallothermic (calcium hydride) synthesis of Ti-Nb alloy powders alloyed with tantalum and zirconium is experimentally studied under various conditions. Chemical, X-ray diffraction, and metallographic analyses of the synthesized products show that initial oxides are completely reduced and a homogeneous β-Ti-based alloy powder forms under the optimum synthesis conditions at a temperature of 1200°C. At a lower synthesis temperature, the end products have a high oxygen content. The experimental results are used to plot the thermokinetic dependences o formation of a bcc solid solution at various times of isothermal holding of Ti-22Nb-6Ta and Ti-22Nb-6Zr (at %) alloys. The physicochemical and technological properties of the Ti-22Nb-6Ta and Ti-22Nb-6Zr alloy powders synthesized by calcium hydride reduction under the optimum conditions are determined.

Preparation and X-ray diffraction studies of curium hydrides

NASA Astrophysics Data System (ADS)

Gibson, J. K.; Haire, R. G.

1985-10-01

Curium hydrides were prepared by reaction of curium-248 metal with hydrogen and characterized by X-ray powder diffraction. Several of the syntheses resulted in a hexagonal compound with average lattice parameters of a0 = 0.3769(8) nm and c0 = 0.6732(12) nm. These products are considered to be CmH 3-δ by analogy with the behavior of lanthanide-hydrogen and lighter actinide-hydrogen systems. Face-centered cubic products with an average lattice parameter of a0 = 0.5322(4) nm were obtained from other curium hydride preparations. This parameter is slightly smaller than that reported previously for cubic curium dihydride, CmH 2+ x (B. M. Bansal and D. Damien, Inorg. Nucl. Chem. Lett., 6, 603, 1970). The present results established a continuation of typical heavy trivalent lanthanide-like behavior of the transuranium actinide-hydrogen systems through curium.

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

DOEpatents

Crisler, L.R.

1975-11-11

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

Hydrogen storage properties of nano-structural carbon and metal hydrides composites

NASA Astrophysics Data System (ADS)

Miyaoka, Hiroki; Ichikawa, Takayuki; Isobe, Shigehito; Fujii, Hironobu

2006-08-01

Thermodynamic and structural properties of some ball-milled mixtures composed of the hydrogenated nanostructural carbon (C nanoH x) and metal hydride (MH; M=Li, Na, Mg and Ca) were examined from thermal desoroption mass spectroscopy and powder X-ray diffraction, respectively. The results showed that the hydrogen desorption temperatures are significantly lowered from those of each hydride (C nanoH x, MH) in the composites. This indicates that a new type of interaction exists between C nanoH x and MH, which destabilizes C-H and/or M-H bonding as well. Therefore, the above Metal-C-H system would be recognized as a new family of hydrogen storage materials.

Approaches to the automatic generation and control of finite element meshes

NASA Technical Reports Server (NTRS)

Shephard, Mark S.

1987-01-01

The algorithmic approaches being taken to the development of finite element mesh generators capable of automatically discretizing general domains without the need for user intervention are discussed. It is demonstrated that because of the modeling demands placed on a automatic mesh generator, all the approaches taken to date produce unstructured meshes. Consideration is also given to both a priori and a posteriori mesh control devices for automatic mesh generators as well as their integration with geometric modeling and adaptive analysis procedures.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sindelar, R.; Louthan, M.; PNNL, B.

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,more » 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

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

DOE PAGES

Yan, Y.; Qian, S.; Littrell, K.; ...

2015-02-13

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

Speciation analysis of arsenic in biological matrices by automated hydride generation-cryotrapping-atomic absorption spectrometry with multiple microflame quartz tube atomizer (multiatomizer)

PubMed Central

Hernández-Zavala, Araceli; Matoušek, Tomáš; Drobná, Zuzana; Paul, David S.; Walton, Felecia; Adair, Blakely M.; Jiří, Dědina; Thomas, David J.

2008-01-01

Analyses of arsenic (As) species in tissues and body fluids of individuals chronically exposed to inorganic arsenic (iAs) provide essential information about the exposure level and pattern of iAs metabolism. We have previously described an oxidation state-specific analysis of As species in biological matrices by hydride-generation atomic absorption spectrometry (HG-AAS), using cryotrapping (CT) for preconcentration and separation of arsines. To improve performance and detection limits of the method, HG and CT steps are automated and a conventional flame-in-tube atomizer replaced with a recently developed multiple microflame quartz tube atomizer (multiatomizer). In this system, arsines from AsIII-species are generated in a mixture of Tris-HCl (pH 6) and sodium borohydride. For generation of arsines from both AsIII- and AsV-species, samples are pretreated with L-cysteine. Under these conditions, dimethylthioarsinic acid, a newly described metabolite of iAs, does not interfere significantly with detection and quantification of methylated trivalent arsenicals. Analytical performance of the automated HG-CT-AAS was characterized by analyses of cultured cells and mouse tissues that contained mono- and dimethylated metabolites of iAs. The capacity to detect methylated AsIII- and AsV-species was verified, using an in vitro methylation system containing recombinant rat arsenic (+3 oxidation state) methyltransferase and cultured rat hepatocytes treated with iAs. Compared with the previous HG-CT-AAS design, detection limits for iAs and its metabolites have improved significantly with the current system, ranging from 8 to 20 pg. Recoveries of As were between 78 and 117%. The precision of the method was better than 5% for all biological matrices examined. Thus, the automated HG-CT-AAS system provides an effective and sensitive tool for analysis of all major human metabolites of iAs in complex biological matrices. PMID:18677417

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

PubMed

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

2016-02-01

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

Solid State NMR Studies of the Aluminum Hydride Phases

NASA Technical Reports Server (NTRS)

Hwang, Son-Jong; Bowman, R. C., Jr.; Graetz, Jason; Reilly, J. J.

2006-01-01

Several solid state NMR techniques including magic-angle-spinning (MAS) and multiple-quantum (MQ) MAS experiments have been used to characterize various AlH3 samples. MAS-NMR spectra for the 1H and 27Al nuclei have been obtained on a variety of AlH3 samples that include the (beta)- and (gamma)- phases as well as the most stable (alpha)-phase. While the dominant components in these NMR spectra correspond to the aluminum hydride phases, other species were found that include Al metal, molecular hydrogen (H2), as well as peaks that can be assigned to Al-O species in different configurations. The occurrence and concentration of these extraneous components are dependent upon the initial AlH3 phase composition and preparation procedures. Both the (beta)-AlH3 and (gamma)-AlH3 phases were found to generate substantial amounts of Al metal when the materials were stored at room temperature while the (alpha)-phase materials do not exhibit these changes.

Metal hydrides as negative electrode materials for Ni- MH batteries

NASA Astrophysics Data System (ADS)

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

2016-01-01

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

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

PubMed

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

2015-01-01

Synchrotron X-rays have been used to study the oxidation of uranium and uranium hydride when encapsulated in grout and stored in de-ionised water for 10 months. Periodic synchrotron X-ray tomography and X-ray powder diffraction have allowed measurement and identification of the arising corrosion products and the rates of corrosion. The oxidation rates of the uranium metal and uranium hydride were slower than empirically derived rates previously reported for each reactant in an anoxic water system, but without encapsulation in grout. This was attributed to the grout acting as a physical barrier limiting the access of oxidising species to the uranium surface. Uranium hydride was observed to persist throughout the 10 month storage period and industrial consequences of this observed persistence are discussed.

The Development of a Compact Refrigeration System using Metal Hydrides

NASA Astrophysics Data System (ADS)

Bae, Sang-Chul; Ogawa, Masahito; Katsuta, Masafumi

The MH refrigeration systems are regarded as important and compact ones for solving energy and environmental issues. Our purposes are to develop the compact refrigeration system for the vending machine and the show case using MH, and to attain a refrigeration temperature of 243K by using a heat source of 403∼423K. The kinetics of MH hydriding and dehydriding reactions is of importance relative to their practical use as a refrigerator system. The kinetics of the reaction between hydrogen and MHHigh (Ti0.18Zr0.84Cr1.0FeO.7Mn0.3CuO.057)has been followed in this paper. A relatively rapid absorption of hydrogen takes place for values of relative composition to about 0.3∼0.4. It is evident that a hydrogen diffusion plays a minor role during this stage, as that part of the metal not covered by hydride is always in contact with hydrogen. The direct chemical reaction between the hydrogen and the exposed metal surface is therefore postulated as the rate-controlling process. The rate of the reaction then decreases, and for values of relative composition above about 0.8, the reaction becomes slow. After the metal particles have been completely covered by a hydride layer, the transport of materials through the layer by diffusion becomes rate controlling process

Automating the generation of finite element dynamical cores with Firedrake

NASA Astrophysics Data System (ADS)

Ham, David; Mitchell, Lawrence; Homolya, Miklós; Luporini, Fabio; Gibson, Thomas; Kelly, Paul; Cotter, Colin; Lange, Michael; Kramer, Stephan; Shipton, Jemma; Yamazaki, Hiroe; Paganini, Alberto; Kärnä, Tuomas

2017-04-01

The development of a dynamical core is an increasingly complex software engineering undertaking. As the equations become more complete, the discretisations more sophisticated and the hardware acquires ever more fine-grained parallelism and deeper memory hierarchies, the problem of building, testing and modifying dynamical cores becomes increasingly complex. Here we present Firedrake, a code generation system for the finite element method with specialist features designed to support the creation of geoscientific models. Using Firedrake, the dynamical core developer writes the partial differential equations in weak form in a high level mathematical notation. Appropriate function spaces are chosen and time stepping loops written at the same high level. When the programme is run, Firedrake generates high performance C code for the resulting numerics which are executed in parallel. Models in Firedrake typically take a tiny fraction of the lines of code required by traditional hand-coding techniques. They support more sophisticated numerics than are easily achieved by hand, and the resulting code is frequently higher performance. Critically, debugging, modifying and extending a model written in Firedrake is vastly easier than by traditional methods due to the small, highly mathematical code base. Firedrake supports a wide range of key features for dynamical core creation: A vast range of discretisations, including both continuous and discontinuous spaces and mimetic (C-grid-like) elements which optimally represent force balances in geophysical flows. High aspect ratio layered meshes suitable for ocean and atmosphere domains. Curved elements for high accuracy representations of the sphere. Support for non-finite element operators, such as parametrisations. Access to PETSc, a world-leading library of programmable linear and nonlinear solvers. High performance adjoint models generated automatically by symbolically reasoning about the forward model. This poster will present

An iron( ii ) hydride complex of a ligand with two adjacent β-diketiminate binding sites and its reactivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gehring, Henrike; Metzinger, Ramona; Braun, Beatrice

2016-01-13

After lithiation of PYR-H2 (PYR = [(NC(Me)C(H)C(Me)NC6H3(iPr)2)2(C5H3N)]2-) – the precursor of an expanded β-diketiminato ligand system with two binding pockets – with KN(TMS)2 the reaction of the resulting potassium salt with FeBr2 led to a dinuclear iron(II) bromide complex [(PYR)Fe(μ-Br)2Fe] (1). Through treatment with KHBEt3 the bromide ligands could be replaced by hydrides to yield [PYR)Fe2(μ-H)2] (2), a distorted analogue of known β-diketiminato iron hydride complexes, as evidenced by NMR, Mößbauer and X-ray absorption spectroscopy, as well as by its reactivity: for instance, 2 reacts with the proton source lutidinium triflate via protonation of the hydride ligands to form anmore » iron(II) product [(PYR)Fe2(OTf)2] (4), while CO2 inserts into the Fe–H bonds generating the formate complex [(PYR)Fe2(μ-HCOO)2] (5); in the presence of traces of water partial hydrolysis occurs so that [(PYR)Fe2(μ-OH)(μ-HCOO)] (6) is isolated. Altogether, the iron(II) chemistry supported by the PYR2- ligand is distinctly different from the one of nickel(II), where both, the arrangement of the two binding pockets and the additional pyridyl donor led to diverging features as compared with the corresponding system based on the parent β-diketiminato ligand.« less

Low-pressure Structural Modification of Aluminum Hydride

DTIC Science & Technology

2011-02-01

Acknowledgments Use of the National Synchrotron Light Source (NSLS), Brookhaven National Laboratory ( BNL ) was supported by the U.S. Department of Energy...National Synchrotron Light Source (NSLS) of Brookhaven National Laboratory ( BNL ). The spectral resolution of ±4 cm–1 was used for all IR measurements...12 List of Symbols, Abbreviations, and Acronyms Al aluminum AlH3 aluminum hydride BNL Brookhaven National Laboratory EOS equation of

FUEL ELEMENTS FOR NUCLEAR REACTORS AND PROCESS OF MAKING

DOEpatents

Roake, W.E.

1958-08-19

A process is described for producing uranium metal granules for use in reactor fuel elements. The granules are made by suspending powdered uramiunn metal or uranium hydride in a viscous, non-reactive liquid, such as paraffin oil, aad pouring the resulting suspension in droplet, on to a bed of powdered absorbent. In this manner the liquid vehicle is taken up by the sorbent and spherical pellets of uranium metal are obtained. The

Geochemistry of environmentally sensitive trace elements in Permian coals from the Huainan coalfield, Anhui, China

USGS Publications Warehouse

Chen, J.; Liu, Gaisheng; Jiang, M.; Chou, C.-L.; Li, H.; Wu, B.; Zheng, Lingyun; Jiang, D.

2011-01-01

To study the geochemical characteristics of 11 environmentally sensitive trace elements in the coals of the Permian Period from the Huainan coalfield, Anhui province, China, borehole samples of 336 coals, two partings, and four roof and floor mudstones were collected from mineable coal seams. Major elements and selected trace elements were determined by inductively coupled plasma optical emission spectrometry (ICP-OES), inductively coupled plasma mass spectrometry (ICP-MS), and hydride generation atomic absorption spectrometry (HAAS). The depositional environment, abundances, distribution, and modes of occurrence of trace elements were investigated. Results show that clay and carbonate minerals are the principal inorganic constituents in the coals. A lower deltaic plain, where fluvial channel systems developed successively, was the likely depositional environment of the Permian coals in the Huainan coalfield. All major elements have wider variation ranges than those of Chinese coals except for Mg and Fe. The contents of Cr, Co, Ni, and Se are higher than their averages for Chinese coals and world coals. Vertical variations of trace elements in different formations are not significant except for B and Ba. Certain roof and partings are distinctly higher in trace elements than underlying coal bench samples. The modes of occurrence of trace elements vary in different coal seams as a result of different coal-forming environments. Vanadium, Cr, and Th are associated with aluminosilicate minerals, Ba with carbonate minerals, and Cu, Zn, As, Se, and Pb mainly with sulfide minerals. ?? 2011 Elsevier B.V.

Irradiation effects on thermal properties of LWR hydride fuel

NASA Astrophysics Data System (ADS)

Terrani, Kurt; Balooch, Mehdi; Carpenter, David; Kohse, Gordon; Keiser, Dennis; Meyer, Mitchell; Olander, Donald

2017-04-01

Three hydride mini-fuel rods were fabricated and irradiated at the MIT nuclear reactor with a maximum burnup of 0.31% FIMA or ∼5 MWd/kgU equivalent oxide fuel burnup. Fuel rods consisted of uranium-zirconium hydride (U (30 wt%)ZrH1.6) pellets clad inside a LWR Zircaloy-2 tubing. The gap between the fuel and the cladding was filled with lead-bismuth eutectic alloy to eliminate the gas gap and the large temperature drop across it. Each mini-fuel rod was instrumented with two thermocouples with tips that are axially located halfway through the fuel centerline and cladding surface. In-pile temperature measurements enabled calculation of thermal conductivity in this fuel as a function of temperature and burnup. In-pile thermal conductivity at the beginning of test agreed well with out-of-pile measurements on unirradiated fuel and decreased rapidly with burnup.

Mechanisms and energetics of hydride dissociation reactions on surfaces of plasma-deposited silicon thin films

NASA Astrophysics Data System (ADS)

Singh, Tejinder; Valipa, Mayur S.; Mountziaris, T. J.; Maroudas, Dimitrios

2007-11-01

We report results from a detailed analysis of the fundamental silicon hydride dissociation processes on silicon surfaces and discuss their implications for the surface chemical composition of plasma-deposited hydrogenated amorphous silicon (a-Si:H) thin films. The analysis is based on a synergistic combination of first-principles density functional theory (DFT) calculations of hydride dissociation on the hydrogen-terminated Si(001)-(2×1) surface and molecular-dynamics (MD) simulations of adsorbed SiH3 radical precursor dissociation on surfaces of MD-grown a-Si :H films. Our DFT calculations reveal that, in the presence of fivefold coordinated surface Si atoms, surface trihydride species dissociate sequentially to form surface dihydrides and surface monohydrides via thermally activated pathways with reaction barriers of 0.40-0.55eV. The presence of dangling bonds (DBs) results in lowering the activation barrier for hydride dissociation to 0.15-0.20eV, but such DB-mediated reactions are infrequent. Our MD simulations on a-Si :H film growth surfaces indicate that surface hydride dissociation reactions are predominantly mediated by fivefold coordinated surface Si atoms, with resulting activation barriers of 0.35-0.50eV. The results are consistent with experimental measurements of a-Si :H film surface composition using in situ attenuated total reflection Fourier transform infrared spectroscopy, which indicate that the a-Si :H surface is predominantly covered with the higher hydrides at low temperatures, while the surface monohydride, SiH(s ), becomes increasingly more dominant as the temperature is increased.

Body centered cubic magnesium niobium hydride with facile room temperature absorption and four weight percent reversible capacity.

PubMed

Tan, XueHai; Wang, Liya; Holt, Chris M B; Zahiri, Beniamin; Eikerling, Michael H; Mitlin, David

2012-08-21

We have synthesized a new metastable metal hydride with promising hydrogen storage properties. Body centered cubic (bcc) magnesium niobium hydride (Mg(0.75)Nb(0.25))H(2) possesses 4.5 wt% hydrogen gravimetric density, with 4 wt% being reversible. Volumetric hydrogen absorption measurements yield an enthalpy of hydride formation of -53 kJ mol(-1) H(2), which indicates a significant thermodynamic destabilization relative to the baseline -77 kJ mol(-1) H(2) for rutile MgH(2). The hydrogenation cycling kinetics are remarkable. At room temperature and 1 bar hydrogen it takes 30 minutes to absorb a 1.5 μm thick film at sorption cycle 1, and 1 minute at cycle 5. Reversible desorption is achieved in about 60 minutes at 175 °C. Using ab initio calculations we have examined the thermodynamic stability of metallic alloys with hexagonal close packed (hcp) versus bcc crystal structure. Moreover we have analyzed the formation energies of the alloy hydrides that are bcc, rutile or fluorite.

Impact of distal mutations on the network of coupled motions correlated to hydride transfer in dihydrofolate reductase.

PubMed

Wong, Kim F; Selzer, Tzvia; Benkovic, Stephen J; Hammes-Schiffer, Sharon

2005-05-10

A comprehensive analysis of the network of coupled motions correlated to hydride transfer in dihydrofolate reductase is presented. Hybrid quantum/classical molecular dynamics simulations are combined with a rank correlation analysis method to extract thermally averaged properties that vary along the collective reaction coordinate according to a prescribed target model. Coupled motions correlated to hydride transfer are identified throughout the enzyme. Calculations for wild-type dihydrofolate reductase and a triple mutant, along with the associated single and double mutants, indicate that each enzyme system samples a unique distribution of coupled motions correlated to hydride transfer. These coupled motions provide an explanation for the experimentally measured nonadditivity effects in the hydride transfer rates for these mutants. This analysis illustrates that mutations distal to the active site can introduce nonlocal structural perturbations and significantly impact the catalytic rate by altering the conformational motions of the entire enzyme and the probability of sampling conformations conducive to the catalyzed reaction.

The crystallography of hydride formation in zirconium: II. the δ → ɛ transformation

NASA Astrophysics Data System (ADS)

Cassidy, M. P.; Wayman, C. M.

1980-12-01

The phenomenological crystallographic theory of martensitic transformations has been applied to the transformation from δ (fcc) to ɛ (fct) zirconium hydride, using published lattice parameters. The habit plane, orientation relationship, lattice invariant shear, and interface characteristics were determined by transmission electron microscopy and diffraction. The shape strain was observed by interference microscopy. Good agreement between the predictions of the theory and the measured crystallography was obtained. The predicted and observed lattice invariant shear was twinning on 101. These twins which are found within alternating bands of hydride variants produce a herringbone morphology, and the bands produce a roof gable type of surface relief. For a given plate, the measured habit plane, twin plane, unique Bain contraction axis, and orientation relationship were mutually consistent with the respective predictions for a single variant. The magnitude of the lattice invariant shear was in excellent agreement with the predicted value. The interfaces separating the e hydride bands were found to be of two types, which alternated, often filling an entire grain. One of these, termed a spear interface, was found to be a twin plane, across which the twinned regions of the two bands “matched-up”. The other, termed an impingement interface, was found to have twin regions which did not “match-up”. This morphology can be explained as a pair of ɛ-hydride plates which share a spear interface. When two growing spears impinge, the resulting impingement interface is of the second type.

Nickel metal hydride LEO cycle testing

NASA Technical Reports Server (NTRS)

Lowery, Eric

1995-01-01

The George C. Marshall Space Flight Center is working to characterize aerospace AB5 Nickel Metal Hydride (NiMH) cells. The cells are being evaluated in terms of storage, low earth orbit (LEO) cycling, and response to parametric testing (high rate charge and discharge, charge retention, pulse current ability, etc.). Cells manufactured by Eagle Picher are the subjects of the evaluation. There is speculation that NiMH cells may become direct replacements for current Nickel Cadmium cells in the near future.

Development of nickel-metal hydride cell

NASA Technical Reports Server (NTRS)

Kuwajima, Saburo; Kamimori, Nolimits; Nakatani, Kensuke; Yano, Yoshiaki

1993-01-01

National Space Development Agency of Japan (NASDA) has conducted the research and development (R&D) of battery cells for space use. A new R&D program about a Nickel-Metal Hydride (Ni-MH) cell for space use from this year, based on good results in evaluations of commercial Ni-MH cells in Tsukuba Space Center (TKSC), was started. The results of those commercial Ni-MH cell's evaluations and recent status about the development of Ni-MH cells for space use are described.

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

NASA Astrophysics Data System (ADS)

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.

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

PubMed Central

Harker, N. J.; Hallam, K. R.; Paraskevoulakos, C.; Banos, A.; Rennie, S.; Jowsey, J.

2015-01-01

Synchrotron X-rays have been used to study the oxidation of uranium and uranium hydride when encapsulated in grout and stored in de-ionised water for 10 months. Periodic synchrotron X-ray tomography and X-ray powder diffraction have allowed measurement and identification of the arising corrosion products and the rates of corrosion. The oxidation rates of the uranium metal and uranium hydride were slower than empirically derived rates previously reported for each reactant in an anoxic water system, but without encapsulation in grout. This was attributed to the grout acting as a physical barrier limiting the access of oxidising species to the uranium surface. Uranium hydride was observed to persist throughout the 10 month storage period and industrial consequences of this observed persistence are discussed. PMID:26176551

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

NASA Technical Reports Server (NTRS)

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.

Systems of Generators for the Normalizers of Certain Elements of the Braid Group

NASA Astrophysics Data System (ADS)

Gurzo, G. G.

1985-06-01

Systems of generators of normalizers are determined for certain elements of the braid group {\\mathfrak{B}}_{n+1}. These systems of generators consist of fewer than 2n explicitly written words in the positive alphabet of {\\mathfrak{B}}_{n+1}. Bibliography: 10 titles.

Sequential patterns of essential trace elements composition in Gracilaria verrucosa and its generated products

NASA Astrophysics Data System (ADS)

Izzati, Munifatul; Haryanti, Sri; Parman, Sarjana

2018-05-01

Gracilaria widely known as a source of essential trace elements. However this red seaweeds also has great potential for being developed into commercial products. This study examined the sequential pattern of essential trace elements composition in fresh Gracilaria verrucosa and a selection of its generated products, nemely extracted agar, Gracilaria salt and Gracilaria residue. The sample was collected from a brackish water pond, located in north part Semarang, Central Java. The collected sample was then dried under the sun, and subsequently processed into aformentioned generated products. The Gracilaria salt was obtain by soaking the sun dried Gracilaria overnight in fresh water overnight. The resulted salt solution was then boiled leaving crystal salt. Extracted agar was obtained with alkali agar extraction method. The rest of remaining material was considered as Gracilaria residue. The entire process was repeated 3 times. The compositin of trace elements was examined using ICP-MS Spectrometry. Collected data was then analyzed by ANOVA single factor. Resulting sequential pattern of its essential trace elements composition was compared. A regular table salt was used as controls. Resuts from this study revealed that Gracilaria verrucosa and its all generated products all have similarly patterned the composition of essential trace elements, where Mn>Zn>Cu>Mo. Additionally this pattern is similar to different subspecies of Gracilaria from different location and and different season. However, Gracilaria salt has distinctly different pattern of sequential essential trace elements composition compared to table salt.

Tuning the Oxidation State, Nuclearity, and Chemistry of Uranium Hydrides with Phenylsilane and Temperature: The Case of the Classic Uranium(III) Hydride Complex [(C 5 Me 5) 2U(μ-H)] 2

DOE PAGES

Pagano, Justin K.; Dorhout, Jacquelyn M.; Czerwinski, Kenneth R.; ...

2016-03-18

Here, this work demonstrates that the oxidation state and chemistry of uranium hydrides can be tuned with temperature and the stoichiometry of phenylsilane. The trivalent uranium hydride [(C 5Me 5) 2U–H] x (5) was found to be comprised of an equilibrium mixture of U(III) hydrides in solution at ambient temperature. A single U(III) species can be selectively prepared by treating (C 5Me5)2UMe2 (4) with 2 equiv of phenylsilane at 50 °C. The U(III) system is a potent reducing agent and displayed chemistry distinct from the U(IV) system [(C 5Me 5) 2U(H)(μ-H)] 2 (2), which was harnessed to prepare a varietymore » of organometallic complexes, including (C 5Me 5) 2U(dmpe)(H) (6), and the novel uranium(IV) metallacyclopentadiene complex (C 5Me 5) 2U(C 4Me 4) (11).« less

Hydrogen mobility in the lightest reversible metal hydride, LiBeH 3

DOE PAGES

Mamontov, Eugene; Kolesnikov, Alexander I.; Sampath, Sujatha; ...

2017-11-24

Lithium-beryllium metal hydrides, which are structurally related to their parent compound, BeH 2, offer the highest hydrogen storage capacity by weight among the metal hydrides (15.93 wt. % of hydrogen for LiBeH 3). Challenging synthesis protocols have precluded conclusive determination of their crystallographic structure to date, but here we analyze directly the hydrogen hopping mechanisms in BeH 2 and LiBeH 3 using quasielastic neutron scattering, which is especially sensitive to single-particle dynamics of hydrogen. We find that, unlike its parent compound BeH 2, lithium-beryllium hydride LiBeH 3 exhibits a sharp increase in hydrogen mobility above 265 K, so dramatic thatmore » it can be viewed as melting of hydrogen sublattice. We perform comparative analysis of hydrogen jump mechanisms observed in BeH 2 and LiBeH 3 over a broad temperature range. As microscopic diffusivity of hydrogen is directly related to its macroscopic kinetics, a transition in LiBeH 3 so close to ambient temperature may offer a straightforward and effective mechanism to influence hydrogen uptake and release in this very lightweight hydrogen storage compound.« less

Hydrogen mobility in the lightest reversible metal hydride, LiBeH 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mamontov, Eugene; Kolesnikov, Alexander I.; Sampath, Sujatha

Lithium-beryllium metal hydrides, which are structurally related to their parent compound, BeH 2, offer the highest hydrogen storage capacity by weight among the metal hydrides (15.93 wt. % of hydrogen for LiBeH 3). Challenging synthesis protocols have precluded conclusive determination of their crystallographic structure to date, but here we analyze directly the hydrogen hopping mechanisms in BeH 2 and LiBeH 3 using quasielastic neutron scattering, which is especially sensitive to single-particle dynamics of hydrogen. We find that, unlike its parent compound BeH 2, lithium-beryllium hydride LiBeH 3 exhibits a sharp increase in hydrogen mobility above 265 K, so dramatic thatmore » it can be viewed as melting of hydrogen sublattice. We perform comparative analysis of hydrogen jump mechanisms observed in BeH 2 and LiBeH 3 over a broad temperature range. As microscopic diffusivity of hydrogen is directly related to its macroscopic kinetics, a transition in LiBeH 3 so close to ambient temperature may offer a straightforward and effective mechanism to influence hydrogen uptake and release in this very lightweight hydrogen storage compound.« less

Preparation and X-Ray diffraction studies of curium hydrides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gibson, J.K.; Maire, R.G.

Curium hydrides were prepared by reaction of curium-248 metal with hydrogen and characterized by X-ray powder diffraction. Several of the syntheses resulted in a hexagonal compound with average lattice parameters of a/sub 0/ = 0.3769(8) nm and c/sub 0/ = 0.6732(12) nm. These products are considere to be CmH/sub 3//sup -//sub 8/ by analogy with the behavior of lanthanide-hydrogen and lighter actinide-hydrogen systems. Face-centered cubic products with an average lattice parameter of a/sub 0/ = 0.5322(4) nm were obtained from other curium hydride preparations. This parameter is slightly smaller than that reported previously for cubic curium dihydride, CmH /SUB 2-x/more » (B.M. Bansal and D. Damien. Inorg. Nucl. Chem. Lett. 6 603, 1970). The present results established a continuation of typical heavy trivalent lanthanidelike behavior of the transuranium actinide-hydrogen systems through curium.« less

Quantifying uncertainty in measurement of mercury in suspended particulate matter by cold vapor technique using atomic absorption spectrometry with hydride generator.

PubMed

Singh, Nahar; Ahuja, Tarushee; Ojha, Vijay Narain; Soni, Daya; Tripathy, S Swarupa; Leito, Ivo

2013-01-01

As a result of rapid industrialization several chemical forms of organic and inorganic mercury are constantly introduced to the environment and affect humans and animals directly. All forms of mercury have toxic effects; therefore accurate measurement of mercury is of prime importance especially in suspended particulate matter (SPM) collected through high volume sampler (HVS). In the quantification of mercury in SPM samples several steps are involved from sampling to final result. The quality, reliability and confidence level of the analyzed data depends upon the measurement uncertainty of the whole process. Evaluation of measurement uncertainty of results is one of the requirements of the standard ISO/IEC 17025:2005 (European Standard EN IS/ISO/IEC 17025:2005, issue1:1-28, 2006). In the presented study the uncertainty estimation in mercury determination in suspended particulate matter (SPM) has been carried out using cold vapor Atomic Absorption Spectrometer-Hydride Generator (AAS-HG) technique followed by wet chemical digestion process. For the calculation of uncertainty, we have considered many general potential sources of uncertainty. After the analysis of data of seven diverse sites of Delhi, it has been concluded that the mercury concentration varies from 1.59 ± 0.37 to 14.5 ± 2.9 ng/m(3) with 95% confidence level (k = 2).

Determination and Uncertainty Analysis of Inorganic Arsenic in Husked Rice by Solid Phase Extraction and Atomic Absorption Spectrometry with Hydride Generation.

PubMed

Saxena, Sushil Kumar; Karipalli, Agnes Raju; Krishnan, Anoop A; Rangasamy, Rajesh; Malekadi, Praveen; Singh, Dhirendra P; Vasu, Vimesh; Singh, Vijay K

2017-05-01

This study enables the selective determination of inorganic arsenic (iAs) with a low detection limit using an economical instrument [atomic absorption spectrometer with hydride generation (HG)] to meet the regulatory requirements as per European Commission (EC) and Codex guidelines. Dry rice samples (0.5 g) were diluted using 0.1 M HNO3-3% H2O2 and heated in a water bath (90 ± 2°C) for 60 min. Through this process, all the iAs is solubilized and oxidized to arsenate [As(V)]. The centrifuged extract was loaded onto a preconditioned and equilibrated strong anion-exchange SPE column (silica-based Strata SAX 500 mg/6 mL), followed by selective and sequential elution of As(V), enabling the selective quantification of iAs using atomic absorption spectrometry with HG. In-house validation showed a mean recovery of 94% and an LOQ of 0.025 mg/kg. The repeatability (HorRatr) and reproducibility (HorRatR) values were <2, meeting the performance criteria mandated by the EC. The combined standard measurement uncertainty by this method was less than the maximum standard measurement uncertainty; thus, the method can be considered for official control purposes. The method was applied for the determination of iAs in husked rice samples and has potential applications in other food commodities.

Method of production of pure hydrogen near room temperature from aluminum-based hydride materials

DOEpatents

Pecharsky, Vitalij K.; Balema, Viktor P.

2004-08-10

The present invention provides a cost-effective method of producing pure hydrogen gas from hydride-based solid materials. The hydride-based solid material is mechanically processed in the presence of a catalyst to obtain pure gaseous hydrogen. Unlike previous methods, hydrogen may be obtained from the solid material without heating, and without the addition of a solvent during processing. The described method of hydrogen production is useful for energy conversion and production technologies that consume pure gaseous hydrogen as a fuel.

Experimental Evidence for a Hydride Transfer Mechanism in Plant Glycolate Oxidase Catalysis*

PubMed Central

Dellero, Younès; Mauve, Caroline; Boex-Fontvieille, Edouard; Flesch, Valérie; Jossier, Mathieu; Tcherkez, Guillaume; Hodges, Michael

2015-01-01

In plants, glycolate oxidase is involved in the photorespiratory cycle, one of the major fluxes at the global scale. To clarify both the nature of the mechanism and possible differences in glycolate oxidase enzyme chemistry from C3 and C4 plant species, we analyzed kinetic parameters of purified recombinant C3 (Arabidopsis thaliana) and C4 (Zea mays) plant enzymes and compared isotope effects using natural and deuterated glycolate in either natural or deuterated solvent. The 12C/13C isotope effect was also investigated for each plant glycolate oxidase protein by measuring the 13C natural abundance in glycolate using natural or deuterated glycolate as a substrate. Our results suggest that several elemental steps were associated with an hydrogen/deuterium isotope effect and that glycolate α-deprotonation itself was only partially rate-limiting. Calculations of commitment factors from observed kinetic isotope effect values support a hydride transfer mechanism. No significant differences were seen between C3 and C4 enzymes. PMID:25416784

Effects of alloy chemistry on the electrochemical and hydriding properties of nickel-substituted lanthanum nickel

NASA Astrophysics Data System (ADS)

Witham, Charles Kincaid

The primary goal of this work was to verify the hypothesis that alloying LaNi5 with ternary elements that have a large heat of formation with La (and secondarily, with Ni) would slow the kinetics of metal (La) atom diffusion. This would have the effect of stabilizing the Haucke phase crystal structure of LaNi5 during electrochemical and gas-phase hydrogen absorption/desorption cycling, and extending the material's useful lifetime. To test this hypothesis, I prepared a variety of single-phase alloys of composition LaNi5-xMx, 0 ≤ x ≤ 0.5, M∈ {Al, Si, Ga, Ge, In, Sn}. Each alloy was annealed to insure equilibrium starting conditions. The lifetimes of these alloys were tested by charge-discharge cycling as the anode of an alkaline Ni-MH rechargeable cell. By characterizing the lifetimes of the alloys as an exponential capacity decay, I was able to determine a trend between the capacity decay and the heat of formation of an average 'B' element with La. The alloys were further characterized by obtaining gas-phase isotherms and, in the case of the Gex alloys, the thermodynamics of metal hydride formation and decomposition. X-ray diffraction was used to measure the effect of substitution on the alloy and its hydride phase. By examining the data obtained at Caltech as well as data published in the literature, several trends were noted. There is a fairly linear relationship between the solute's expansion of the LaNi5 unit cell and its radius. The total volume expansion an alloy experienced upon absorption of hydrogen was found to decrease with substituted composition. The discrete lattice expansion of Gex alloys was found to decrease substantially for 0 < x < 0.2, but subsequent substitution had little effect on the volume expansion. The electrode electrochemical kinetice of charge transfer were investigated for each MH alloy. Measurements of the charge transfer exchange current by micropolarization and AC impedance were similar, while those measured by Tafel

Unconstrained paving and plastering method for generating finite element meshes

DOEpatents

Staten, Matthew L.; Owen, Steven J.; Blacker, Teddy D.; Kerr, Robert

2010-03-02

Computer software for and a method of generating a conformal all quadrilateral or hexahedral mesh comprising selecting an object with unmeshed boundaries and performing the following while unmeshed voids are larger than twice a desired element size and unrecognizable as either a midpoint subdividable or pave-and-sweepable polyhedra: selecting a front to advance; based on sizes of fronts and angles with adjacent fronts, determining which adjacent fronts should be advanced with the selected front; advancing the fronts; detecting proximities with other nearby fronts; resolving any found proximities; forming quadrilaterals or unconstrained columns of hexahedra where two layers cross; and establishing hexahedral elements where three layers cross.

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

PubMed

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

2012-01-19

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

Process of forming a sol-gel/metal hydride composite

DOEpatents

Congdon, James W [Aiken, SC

2009-03-17

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

Automated Generation of Finite-Element Meshes for Aircraft Conceptual Design

NASA Technical Reports Server (NTRS)

Li, Wu; Robinson, Jay

2016-01-01

This paper presents a novel approach for automated generation of fully connected finite-element meshes for all internal structural components and skins of a given wing-body geometry model, controlled by a few conceptual-level structural layout parameters. Internal structural components include spars, ribs, frames, and bulkheads. Structural layout parameters include spar/rib locations in wing chordwise/spanwise direction and frame/bulkhead locations in longitudinal direction. A simple shell thickness optimization problem with two load conditions is used to verify versatility and robustness of the automated meshing process. The automation process is implemented in ModelCenter starting from an OpenVSP geometry and ending with a NASTRAN 200 solution. One subsonic configuration and one supersonic configuration are used for numerical verification. Two different structural layouts are constructed for each configuration and five finite-element meshes of different sizes are generated for each layout. The paper includes various comparisons of solutions of 20 thickness optimization problems, as well as discussions on how the optimal solutions are affected by the stress constraint bound and the initial guess of design variables.

Extracting More Information from Passive Optical Tracking Observations for Reliable Orbit Element Generation

NASA Astrophysics Data System (ADS)

Bennett, J.; Gehly, S.

2016-09-01

This paper presents results from a preliminary method for extracting more orbital information from low rate passive optical tracking data. An improvement in the accuracy of the observation data yields more accurate and reliable orbital elements. A comparison between the orbit propagations from the orbital element generated using the new data processing method is compared with the one generated from the raw observation data for several objects. Optical tracking data collected by EOS Space Systems, located on Mount Stromlo, Australia, is fitted to provide a new orbital element. The element accuracy is determined from a comparison between the predicted orbit and subsequent tracking data or reference orbit if available. The new method is shown to result in a better orbit prediction which has important implications in conjunction assessments and the Space Environment Research Centre space object catalogue. The focus is on obtaining reliable orbital solutions from sparse data. This work forms part of the collaborative effort of the Space Environment Management Cooperative Research Centre which is developing new technologies and strategies to preserve the space environment (www.serc.org.au).

MIS High-Purity Plutonium Oxide Hydride Product 5501579 (SSR124): Final Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Veirs, Douglas Kirk; Stroud, Mary Ann; Berg, John M.

A high-purity plutonium dioxide material from the Material Identification and Surveillance (MIS) Program inventory has been studied with regard to gas generation and corrosion in a storage environment. Sample 5501579 represents process plutonium oxides from hydride oxide from Rocky Flats that are currently stored in 3013 containers. After calcination to 950°C, the material contained 87.42% plutonium with no major impurities. This study followed over time, the gas pressure of a sample with nominally 0.5 wt% water in a sealed container with an internal volume scaled to 1/500th of the volume of a 3013 container. Gas compositions were measured periodically overmore » a six year period. The maximum observed gas pressure was 124 kPa. The increase over the initial pressure of 70 kPa was primarily due to generation of nitrogen and carbon dioxide gas. Hydrogen and oxygen were minor components of the headspace gas. At the completion of the study, the internal components of the sealed container showed signs of corrosion.« less

Multi-scale characterization of nanostructured sodium aluminum hydride

NASA Astrophysics Data System (ADS)

NaraseGowda, Shathabish

Complex metal hydrides are the most promising candidate materials for onboard hydrogen storage. The practicality of this class of materials is counter-poised on three critical attributes: reversible hydrogen storage capacity, high hydrogen uptake/release kinetics, and favorable hydrogen uptake/release thermodynamics. While a majority of modern metallic hydrides that are being considered are those that meet the criteria of high theoretical storage capacity, the challenges lie in addressing poor kinetics, thermodynamics, and reversibility. One emerging strategy to resolve these issues is via nanostructuring or nano-confinement of complex hydrides. By down-sizing and scaffolding them to retain their nano-dimensions, these materials are expected to improve in performance and reversibility. This area of research has garnered immense interest lately and there is active research being pursued to address various aspects of nanostructured complex hydrides. The research effort documented here is focused on a detailed investigation of the effects of nano-confinement on aspects such as the long range atomic hydrogen diffusivities, localized hydrogen dynamics, microstructure, and dehydrogenation mechanism of sodium alanate. A wide variety of microporous and mesoporous materials (metal organic frameworks, porous silica and alumina) were investigated as scaffolds and the synthesis routes to achieve maximum pore-loading are discussed. Wet solution infiltration technique was adopted using tetrahydrofuran as the medium and the precursor concentrations were found to have a major role in achieving maximum pore loading. These concentrations were optimized for each scaffold with varying pore sizes and confinement was quantitatively characterized by measuring the loss in specific surface area. This work is also aimed at utilizing neutron and synchrotron x-ray characterization techniques to study and correlate multi-scale material properties and phenomena. Some of the most advanced

Quasi-automatic 3D finite element model generation for individual single-rooted teeth and periodontal ligament.

PubMed

Clement, R; Schneider, J; Brambs, H-J; Wunderlich, A; Geiger, M; Sander, F G

2004-02-01

The paper demonstrates how to generate an individual 3D volume model of a human single-rooted tooth using an automatic workflow. It can be implemented into finite element simulation. In several computational steps, computed tomography data of patients are used to obtain the global coordinates of the tooth's surface. First, the large number of geometric data is processed with several self-developed algorithms for a significant reduction. The most important task is to keep geometrical information of the real tooth. The second main part includes the creation of the volume model for tooth and periodontal ligament (PDL). This is realized with a continuous free form surface of the tooth based on the remaining points. Generating such irregular objects for numerical use in biomechanical research normally requires enormous manual effort and time. The finite element mesh of the tooth, consisting of hexahedral elements, is composed of different materials: dentin, PDL and surrounding alveolar bone. It is capable of simulating tooth movement in a finite element analysis and may give valuable information for a clinical approach without the restrictions of tetrahedral elements. The mesh generator of FE software ANSYS executed the mesh process for hexahedral elements successfully.

Electronic structure and magnetic ordering in manganese hydride

NASA Astrophysics Data System (ADS)

Magnitskaya, M. V.; Kulikov, N. I.

1991-03-01

The self-consistent electron energy bands of antiferromagnetic (AFM) and non-magnetic manganese hydride are calculated using the linear muffintin orbital method (LMTO). The calculated values of equilibrium volume and of magnetic moment on the manganese site are in good agreement with experiment. The Fermi surface of paramagnetic MnH contains two nesting parts, and their superposition gives rise to AFM gap.

A parallel algorithm for generation and assembly of finite element stiffness and mass matrices

NASA Technical Reports Server (NTRS)

Storaasli, O. O.; Carmona, E. A.; Nguyen, D. T.; Baddourah, M. A.

1991-01-01

A new algorithm is proposed for parallel generation and assembly of the finite element stiffness and mass matrices. The proposed assembly algorithm is based on a node-by-node approach rather than the more conventional element-by-element approach. The new algorithm's generality and computation speed-up when using multiple processors are demonstrated for several practical applications on multi-processor Cray Y-MP and Cray 2 supercomputers.

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

NASA Technical Reports Server (NTRS)

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.

[The progress in speciation analysis of trace elements by atomic spectrometry].

PubMed

Wang, Zeng-Huan; Wang, Xu-Nuo; Ke, Chang-Liang; Lin, Qin

2013-12-01

The main purpose of the present work is to review the different non-chromatographic methods for the speciation analysis of trace elements in geological, environmental, biological and medical areas. In this paper, the sample processing methods in speciation analysis were summarized, and the main strategies for non-chromatographic technique were evaluated. The basic principles of the liquid extractions proposed in the published literatures recently and their advantages and disadvantages were discussed, such as conventional solvent extraction, cloud point extraction, single droplet microextraction, and dispersive liquid-liquid microextraction. Solid phase extraction, as a non-chromatographic technique for speciation analysis, can be used in batch or in flow detection, and especially suitable for the online connection to atomic spectrometric detector. The developments and applications of sorbent materials filled in the columns of solid phase extraction were reviewed. The sorbents include chelating resins, nanometer materials, molecular and ion imprinted materials, and bio-sorbents. Other techniques, e. g. hydride generation technique and coprecipitation, were also reviewed together with their main applications.

A study of H+ production using metal hydride and other compounds by means of laser ion source

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sekine M.; Kondo K.; Okamura, M.

2012-02-22

A laser ion source can provide wide variety of ion beams from solid target materials, however, it has been difficult to create proton beam efficiently. We examined capability of proton production using beeswax, polyethylene, and metal hydrides (MgH2 and ZrH2) as target materials. The results showed that beeswax and polyethylene could not be used to produce protons because these targets are transparent to the laser wavelength of 1064 nm. On the other hand, the metal hydrides could supply protons. Although the obtained particle numbers of protons were less than those of the metal ions, the metal hydrides could be usedmore » as a target for proton laser ion source.« less

Reactivity of Hydride Bridges in High-Spin [3M-3(μ-H)] Clusters (M = FeII, CoII).

PubMed

Lee, Yousoon; Anderton, Kevin J; Sloane, Forrest T; Ermert, David M; Abboud, Khalil A; García-Serres, Ricardo; Murray, Leslie J

2015-08-26

The designed [3M-3(μ-H)] clusters (M = Fe(II), Co(II)) Fe3H3L (1-H) and Co3H3L (2-H) [where L(3-) is a tris(β-diketiminate) cyclophane] were synthesized by treating the corresponding M3Br3L complexes with KBEt3H. From single-crystal X-ray analysis, the hydride ligands are sterically protected by the cyclophane ligand, and these complexes selectively react with CO2 over other unsaturated substrates (e.g., CS2, Me3SiCCH, C2H2, and CH3CN). The reaction of 1-H or 2-H with CO2 at room temperature yielded Fe3(OCHO)(H)2L (1-CO2) or Co3(OCHO)(H)2L (2-CO2), respectively, which evidence the differential reactivity of the hydride ligands within these complexes. The analogous reactions at elevated temperatures revealed a distinct difference in the reactivity pattern for 2-H as compared to 1-H; Fe3(OCHO)3L (1-3CO2) was generated from 1-H, while 2-H afforded only 2-CO2.

Speciation of selenium and arsenic compounds by capillary electrophoresis with hydrodynamically modified electroosmotic flow and on-line reduction of selenium(VI) to selenium(IV) with hydride generation inductively coupled plasma mass spectrometric detection.

PubMed

Magnuson, M L; Creed, J T; Brockhoff, C A

1997-10-01

Capillary electrophoresis (CE) with hydride generation inductively coupled plasma mass spectrometry was used to determine four arsenicals and two selenium species. Selenate (SeVI) was reduced on-line to selenite (SeIV) by mixing the CE effluent with concentrated HCl. A microporous PTFE tube was used as a gas-liquid separator to eliminate the 40Ar37Cl and 40Ar35Cl interference from 77Se and 75As, respectively. The direction of the electroosmotic flow during CE was reversed with hydrodynamic pressure, which allowed increased freedom of buffer choice. For conventional pressure injection, method detection limits for SeIV and SeVI based on seven replicate injections were 10 and 24 pg, respectively. Recoveries of SeIV and SeVI in drinking water were measured.

Theoretical study of hydrogen storage in metal hydrides.

PubMed

Oliveira, Alyson C M; Pavão, A C

2018-05-04

Adsorption, absorption and desorption energies and other properties of hydrogen storage in palladium and in the metal hydrides AlH 3 , MgH 2 , Mg(BH 4 ) 2 , Mg(BH 4 )(NH 2 ) and LiNH 2 were analyzed. The DFT calculations on cluster models show that, at a low concentration, the hydrogen atom remains adsorbed in a stable state near the palladium surface. By increasing the hydrogen concentration, the tetrahedral and the octahedral sites are sequentially occupied. In the α phase the tetrahedral site releases hydrogen more easily than at the octahedral sites, but the opposite occurs in the β phase. Among the hydrides, Mg(BH 4 ) 2 shows the highest values for both absorption and desorption energies. The absorption energy of LiNH 2 is higher than that of the palladium, but its desorption energy is too high, a recurrent problem of the materials that have been considered for hydrogen storage. The release of hydrogen, however, can be favored by using transition metals in the material structure, as demonstrated here by doping MgH 2 with 3d and 4d-transition metals to reduce the hydrogen atomic charge and the desorption energy.

Influence of hydride orientation on fracture toughness of CWSR Zr-2.5%Nb pressure tube material between RT and 300 °C

NASA Astrophysics Data System (ADS)

Sharma, Rishi K.; Sunil, Saurav; Kumawat, B. K.; Singh, R. N.; Tewari, Asim; Kashyap, B. P.

2017-05-01

An experimental setup was designed, fabricated and used to form radial hydrides in Zr-2.5%Nb alloy pressure tube spool. The design of setup was based on ensuring a hoop stress in the spool greater than threshold stress for reorientation of hydrides in this alloy, which was achieved by manipulating the thermal expansion coefficient of the plunger and pressure tube material and diametral interference between them. The experimental setup was loaded on a universal testing machine (UTM) fitted with an environmental chamber and subjected to a temperature cycle for the stress reorientation treatment. The metallographic examination of the hydrogen charged spools subjected to stress re-orientation treatment using this set up revealed formation of predominantly radial hydrides. The variation of fracture toughness of material containing radial hydride with test temperature showed typical 'S' curve behavior with transition temperatures more than that of the material containing circumferential hydride.

Future's operation areas: new-generation suppression enemy air defence (SEAD) elements

NASA Astrophysics Data System (ADS)

Hazinedar, Ä.°lker

2015-05-01

Since air vehicles took place in the theater of operations, they have become the indispensable elements and the strongest attack power of armed forces. In the following period, with technological development, supersonic aircrafts took place in the operation area and this increased effectiveness of air vehicles much more. Air forces have used these aircrafts during important missions like strategic attack and air defense operations. On the other hand, decision makers understood that it was not feasible to intercept fighter aircrafts by executing combat air patrol flight missions. Since there is not enough reaction time to intercept the high speed aircrafts, ground stationed Surface to Air Missiles (SAM) system requirement has emerged. Therefore, SAM systems took place in the operation scene as well. Due to the fact that SAM systems emerged against the attack power, the attack aircrafts are to keep away from the fire of the ground stationed SAM systems. Hence, the requirement of Suppression Enemy Air Defense (SEAD) arose. SEAD elements take under suppression the radar of the SAM systems. In this way, attack aircrafts are able to attack without the risk of SAM systems. The purpose of this study is to find new methods or concepts in order to protect friendly attack aircrafts against ground based surface to air missiles' fires. Modernization of SAM systems and new generation SAM system producing activities have proceeded with positive acceleration. So, current SEAD elements and concepts are not able to cover the requirements due to the increased SAM system ranges. According to the concepts, SEAD weapons` ranges must be longer than the SAM weapons' ranges to protect friendly aircrafts. In this study, new concept was offered to overcome the deficiencies of current SEAD concept. The elements of new concepts were put forward. Classic SEAD concept and new generation concepts were assessed by using SWOT analysis technique. As a result, this study has revealed that, air forces

The Hall Effect in Hydrided Rare Earth Films

NASA Astrophysics Data System (ADS)

Koon, D. W.; Azofeifa, D. E.; Clark, N.

We describe two new techniques for measuring the Hall effect in capped rare earth films during hydriding. In one, we simultaneously measure resistivity and the Hall coefficient for a rare earth film covered with four different thicknesses of Pd, recovering the charge transport quantities for both materials. In the second technique, we replace Pd with Mn as the covering layer. We will present results from both techniques.

Selective Reduction of CO2 to a Formate Equivalent with Heterobimetallic Gold- - -Copper Hydride Complexes.

PubMed

Hicken, Alexandra; White, Andrew J P; Crimmin, Mark R

2017-11-20

A series of heterobimetallic complexes containing three-center, two-electron Au-H-Cu bonds have been prepared from addition of a parent gold hydride to a bent d 10 copper(I) fragment. These highly unusual heterobimetallic complexes represent a missing link in the widely investigated series of neutral and cationic coinage metal hydride complexes containing Cu-H-Cu and M-H-M + moieties (M=Cu, Ag). The well-defined heterobimetallic hydride complexes act as precatalysts for the conversion of CO 2 into HCO 2 Bpin with HBpin as the reductant. The selectivity of the heterobimetallic complexes for the catalytic production of a formate equivalent surpasses that of the parent monomeric Group 11 complexes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lactate Racemase Nickel-Pincer Cofactor Operates by a Proton-Coupled Hydride Transfer Mechanism.

PubMed

Rankin, Joel A; Mauban, Robert C; Fellner, Matthias; Desguin, Benoît; McCracken, John; Hu, Jian; Varganov, Sergey A; Hausinger, Robert P

2018-03-09

Lactate racemase (LarA) of Lactobacillus plantarum contains a novel organometallic cofactor with nickel coordinated to a covalently tethered pincer ligand, pyridinium-3-thioamide-5-thiocarboxylic acid mononucleotide, but its function in the enzyme mechanism has not been elucidated. This study presents direct evidence that the nickel-pincer cofactor facilitates a proton-coupled hydride transfer (PCHT) mechanism during LarA-catalyzed lactate racemization. No signal was detected by electron paramagnetic resonance spectroscopy for LarA in the absence or presence of substrate, consistent with a +2 metal oxidation state and inconsistent with a previously proposed proton-coupled electron transfer mechanism. Pyruvate, the predicted intermediate for a PCHT mechanism, was observed in quenched solutions of LarA. A normal substrate kinetic isotope effect ( k H / k D of 3.11 ± 0.17) was established using 2-α- 2 H-lactate, further supporting a PCHT mechanism. UV-visible spectroscopy revealed a lactate-induced perturbation of the cofactor spectrum, notably increasing the absorbance at 340 nm, and demonstrated an interaction of the cofactor with the inhibitor sulfite. A crystal structure of LarA provided greater resolution (2.4 Å) than previously reported and revealed sulfite binding to the pyridinium C4 atom of the reduced pincer cofactor, mimicking hydride reduction during a PCHT catalytic cycle. Finally, computational modeling supports hydride transfer to the cofactor at the C4 position or to the nickel atom, but with formation of a nickel-hydride species requiring dissociation of the His200 metal ligand. In aggregate, these studies provide compelling evidence that the nickel-pincer cofactor acts by a PCHT mechanism.

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

USGS Publications Warehouse

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

2017-01-01

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

Studies on hydride-forming alloys as the active material of a metal hydride electrode for a nickel metal hydride cell

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lim, H.S.; Zelter, G.R.; Allison, D.U.

1997-12-01

Multi-component AB{sub 5} hydrides are attractive replacements for the cadmium electrode in nickel-cadmium batteries. The archetype compound of the AB{sub 5} alloy class is LaNi{sub 5}, but in a typical battery electrode mischmetal is substituted for La and Ni is substituted in part by variety of metals. This paper deals with the effect on cycle life upon the partial substitution of various lanthanides for La and Sn, In, Al, Co, and Mn for Ni. The presence of Ce was shown to enhance cycle life as did Sn in some cases. An electrode of La{sub 0.67}Ce{sub 0.33}B{sub 5} alloy gave overmore » 3,500 cycles (to specific capacity of 200 mAh/g), indicating that it is a very attractive alloy for a practical Ni/MH{sub x} cell.« less

Anisotropic Resistivity Forward Modelling Using Automatic Generated Higher-order Finite Element Codes

NASA Astrophysics Data System (ADS)

Wang, W.; Liu, J.

2016-12-01

Forward modelling is the general way to obtain responses of geoelectrical structures. Field investigators might find it useful for planning surveys and choosing optimal electrode configurations with respect to their targets. During the past few decades much effort has been put into the development of numerical forward codes, such as integral equation method, finite difference method and finite element method. Nowadays, most researchers prefer the finite element method (FEM) for its flexible meshing scheme, which can handle models with complex geometry. Resistivity Modelling with commercial sofewares such as ANSYS and COMSOL is convenient, but like working with a black box. Modifying the existed codes or developing new codes is somehow a long period. We present a new way to obtain resistivity forward modelling codes quickly, which is based on the commercial sofeware FEPG (Finite element Program Generator). Just with several demanding scripts, FEPG could generate FORTRAN program framework which can easily be altered to adjust our targets. By supposing the electric potential is quadratic in each element of a two-layer model, we obtain quite accurate results with errors less than 1%, while more than 5% errors could appear by linear FE codes. The anisotropic half-space model is supposed to concern vertical distributed fractures. The measured apparent resistivities along the fractures are bigger than results from its orthogonal direction, which are opposite of the true resistivities. Interpretation could be misunderstood if this anisotropic paradox is ignored. The technique we used can obtain scientific codes in a short time. The generated powerful FORTRAN codes could reach accurate results by higher-order assumption and can handle anisotropy to make better interpretations. The method we used could be expand easily to other domain where FE codes are needed.

Neutron spectroscopy of γ manganese hydride

NASA Astrophysics Data System (ADS)

Antonov, V. E.; Cornell, K.; Dorner, B.; Fedotov, V. K.; Grosse, G.; Kolesnikov, A. I.; Wagner, F. E.; Wipf, H.

2000-02-01

The vibrational spectrum of fcc γ-MnH 0.41 synthesized under high pressure of gaseous hydrogen was studied by inelastic neutron scattering at 2 K in the range of energy transfers from 25 to 400 meV. The fundamental band of optical hydrogen vibrations consists of a peak at 111 meV with a broad shoulder towards higher energies, which extends up to about 140 meV. At higher energy transfers, the spectrum originates from multiphonon neutron scattering and exhibits approximately harmonic behaviour. The results are compared with the available data for other metal hydrides.

Apparatus and method for heterodyne-generated two-dimensional detector array using a single element detector

DOEpatents

Strauss, Charlie E.

1997-01-01

Apparatus and method for heterodyne-generated, two-dimensional detector array using a single detector. Synthetic-array heterodyne detection, permits a single-element optical detector to behave as though it were divided into an array of separate heterodyne detector elements. A fifteen-element synthetic array has successfully been experimentally realized on a single-element detector, permitting all of the array elements to be read out continuously and in parallel from one electrical connection. A CO.sub.2 laser and a single-element HgCdTe photodiode are employed. A different heterodyne local oscillator frequency is incident upon the spatially resolvable regions of the detector surface. Thus, different regions are mapped to different heterodyne beat frequencies. One can determine where the photons were incident on the detector surface even though a single electrical connection to the detector is used. This also prevents the destructive interference that occurs when multiple speckles are imaged (similar to spatial diversity), In coherent LIDAR this permits a larger field of view. An acoustooptic modulator generates the local oscillator frequencies and can achieve adequate spatial separation of optical frequencies of the order of a megahertz apart.

Apparatus and method for heterodyne-generated two-dimensional detector array using a single element detector

DOEpatents

Strauss, C.E.

1997-11-18

Apparatus and method are disclosed for heterodyne-generated, two-dimensional detector array using a single detector. Synthetic-array heterodyne detection, permits a single-element optical detector to behave as though it were divided into an array of separate heterodyne detector elements. A fifteen-element synthetic array has successfully been experimentally realized on a single-element detector, permitting all of the array elements to be read out continuously and in parallel from one electrical connection. A CO{sub 2} laser and a single-element HgCdTe photodiode are employed. A different heterodyne local oscillator frequency is incident upon the spatially resolvable regions of the detector surface. Thus, different regions are mapped to different heterodyne beat frequencies. One can determine where the photons were incident on the detector surface even though a single electrical connection to the detector is used. This also prevents the destructive interference that occurs when multiple speckles are imaged (similar to spatial diversity), In coherent LIDAR this permits a larger field of view. An acoustooptic modulator generates the local oscillator frequencies and can achieve adequate spatial separation of optical frequencies of the order of a megahertz apart. 4 figs.

Finite Element Analysis Generates an Increasing Interest in Dental Research: A Bibliometric Study.

PubMed

Diarra, Abdoulaziz; Mushegyan, Vagan; Naveau, Adrien

2016-01-01

The purpose was to provide a longitudinal overview of published studies that use finite element analysis in dental research, by using the SCI-expanded database of Web of Science(®) (Thomson Reuters). Eighty publications from 1999-2000 and 473 from 2009-2010 were retrieved. This literature grew faster than the overall dental literature. The number of publishing countries doubled. The main journals were American or English, and dealt with implantology. For the top 10 journals publishing dental finite element papers, the mean impact factor increased by 75% during the decade. Finite elements generate an increasing interest from dental authors and publishers worldwide.

Stream-sediment samples reanalyzed for major, rare earth, and trace elements from seven 1:250,000-scale quadrangles, south-central Alaska, 2007-09

USGS Publications Warehouse

Gamble, Bruce M.; Bailey, Elizabeth A.; Shew, Nora B.; Labay, Keith A.; Schmidt, Jeanine M.; O'Leary, Richard M.; Detra, David E.

2010-01-01

During the 1960s through the 1980s, the U.S. Geological Survey conducted reconnaissance geochemical surveys of drainage basins throughout most of the Iliamna, Lake Clark, Lime Hills, and Talkeetna 1:250,000-scale quadrangles and parts of the McGrath, Seldovia, and Tyonek 1:250,000-scale quadrangles in Alaska. These geochemical surveys provide data necessary to assess the potential for undiscovered mineral resources and provide data that may be used to determine regional-scale element baselines. This report provides new data for 1,075 of the previously collected stream-sediment samples. The new analyses include a broader spectrum of elements and provide data that are more precise than the original analyses. All samples were analyzed for arsenic by hydride generation atomic absorption spectrometry, for gold, palladium, and platinum by inductively coupled plasma-mass spectrometry after lead button fire assay separation, and for a suite of 55 major, rare earth, and trace elements by inductively coupled plasma-atomic emission spectrometry and inductively coupled plasma-mass spectrometry after sodium peroxide sinter at 450 degrees Celsius.

Novel 3-hydroxypropyl bonded phase by direct hydrosilylation of allyl alcohol on amorphous hydride silica

PubMed Central

Gómez, Jorge E.; Navarro, Fabián H.; Sandoval, Junior E.

2015-01-01

A novel 3-hydroxypropyl (propanol) bonded silica phase has been prepared by hydrosilylation of allyl alcohol on a hydride silica intermediate, in the presence of platinum (0)-divinyltetramethyldisiloxane (Karstedt's catalyst). The regio-selectivity of this synthetic approach had been correctly predicted by previous reports involving octakis(dimethylsiloxy)octasilsesquioxane (Q8M8H) and hydrogen silsesquioxane (T8H8), as molecular analogs of hydride amorphous silica. Thus, C-silylation predominated (~ 94%) over O-silylation, and high surface coverages of propanol groups (5±1 µmol/m2) were typically obtained in this work. The propanol-bonded phase was characterized by spectroscopic (IR and solid state NMR on silica microparticles), contact angle (on fused-silica wafers) and CE (on fused-silica tubes) techniques. CE studies of the migration behavior of pyridine, caffeine, tris(2,2’-bipyridine)Ru(II) chloride and lysozyme on propanol-modified capillaries were carried out. The adsorption properties of these select silanol-sensitive solutes were compared to those on the unmodified and hydride-modified tubes. It was found that hydrolysis of the SiH species underlying the immobilized propanol moieties leads mainly to strong ion-exchange based interactions with the basic solutes at pH 4, particularly with lysozyme. Interestingly, and in agreement with water contact angle and electroosmotic mobility figures, the silanol-probe interactions on the buffer-exposed (hydrolyzed) hydride surface are quite different from those of the original unmodified tube. PMID:24934906

Kinetics of the isothermal decomposition of zirconium hydride: terminal solid solubility for precipitation and dissolution

NASA Astrophysics Data System (ADS)

Denisov, E. A.; Kompaniets, T. N.; Voyt, A. P.

2018-05-01

The hydrogen permeation technique in the surface-limited regime (SLR) was first used to study the isothermal decomposition of zirconium hydride. It is shown that under isothermal conditions, the hydrogen terminal solid solubility in the α-phase for hydride precipitation (TSSp) and dissolution (TSSd) differ only by 6%, in contrast to the 20-30% indicated in the available literature. It is demonstrated that even the minimum heating/cooling rate (1 C/min) used in the traditional methods of studying TSSp and TSSd is too high to exclude the effect of kinetics on the results obtained.

Structural stability, electronic structure and mechanical properties of alkali gallium hydrides AGaH{sub 4} (A = Li, Na)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Santhosh, M.; Rajeswarapalanichamy, R., E-mail: rrpalanichamy@gmail.com; Manikandan, M.

2016-05-06

Ab initio calculations are performed to investigate the structural stability, electronic structure and mechanical properties of alkali gallium hydrides AGaH{sub 4} (A = Li, Na) for three different crystal structures, namely tetragonal (P42{sub 1}c), tetragonal (P4{sub 2}/nmc) and monoclinic (P2{sub 1}/c). Among the considered structures, tetragonal (P42{sub 1}c) phase is found to be the most stable phase for these hydrides at normal pressure. A pressure induced structural phase transition from tetragonal (P42{sub 1}c) to tetragonal (P4{sub 2}/nmc) is observed. The electronic structure reveals that these hydrides are insulators. The calculated elastic constants indicate that these ternary imides are mechanically stablemore » at normal pressure.« less

Concentration and distribution of sixty-one elements in coals from DPR Korea

USGS Publications Warehouse

Hu, Jiawen; Zheng, B.; Finkelman, R.B.; Wang, B.; Wang, M.; Li, S.; Wu, D.

2006-01-01

Fifty coal samples (28 anthracite and 22 lignites) were collected from both main and small coal mines in DPR Korea prioritized by resource distribution and coal production. The concentrations of 61 elements in 50 coal samples were determined by several multielement and element-specific techniques, including inductively coupled plasma atomic emission spectrometry (ICP-AES), and inductively coupled plasma mass spectrometry (ICP-MS), ion chromatogram (IC), cold-vapor atomic absorption spectrometry (CV-AAS), and hydride generation atomic absorption spectrometry (HGAAS). The ranges, arithmetic means and geometric means of concentrations of these elements are presented. A comparison with crustal abundances (Clarke values) shows that some potentially hazardous elements in the coals of DPR Korea are highly enriched Li, B, S, Cl, Zn, As, Se, Cd, Sn, Sb, W, Te, Hg, Ag, Pb, and La, Ce, Dy, Tm, Ge, Mo, Cs, Tl, Bi, Th and U are moderately enriched. A comparison of ranges and means of elemental concentrations in DPR Korea, Chinese, and world coals shows the ranges of most elements in DPR Korea coals are very close to the ranges of world coals. Arithmetic means of most elements in DPR Korea coals are close to that of American coals. Most elements arithmetic means are higher in Jurassic and Paleogene coals than coals of other ages. In DPR Korea coals, only seven elements in early Permian coals are higher than other periods: Li, Zn, Se, Cd, Hg, Pb, and Bi. Only five elements B, As, Sr, Mo, W in Neogene coals have arithmetic means higher than others. SiO2 and Al2O 3 in ashes are more than 70% except six samples. The correlation between ash yields and major elements from high to low is in the order of Si>Al>Ti>K>Mg>Fe>Na>Ca>P>S. Most elements have high positive correlation with ash (r>0.5) and show high inorganic affinity. ?? 2005 Elsevier Ltd. All rights reserved.

Borophene hydride: a stiff 2D material with high thermal conductivity and attractive optical and electronic properties.

PubMed

Mortazavi, Bohayra; Makaremi, Meysam; Shahrokhi, Masoud; Raeisi, Mostafa; Singh, Chandra Veer; Rabczuk, Timon; Pereira, Luiz Felipe C

2018-02-22

Two-dimensional (2D) structures of boron atoms, so-called borophene, have recently attracted remarkable attention. In a recent exciting experimental study, a hydrogenated borophene structure was realized. Motivated by this success, we conducted extensive first-principles calculations to explore the mechanical, thermal conduction, electronic and optical responses of borophene hydride. The mechanical response of borophene hydride was found to be anisotropic, with an elastic modulus of 131 N m -1 and a high tensile strength of 19.9 N m -1 along the armchair direction. Notably, it was shown that by applying mechanical loading the metallic electronic character of borophene hydride can be altered to direct band-gap semiconducting, very appealing for application in nanoelectronics. The absorption edge of the imaginary part of the dielectric function was found to occur in the visible range of light for parallel polarization. Finally, it was estimated that this novel 2D structure at room temperature can exhibit high thermal conductivities of 335 W mK -1 and 293 W mK -1 along the zigzag and armchair directions, respectively. Our study confirms that borophene hydride shows an outstanding combination of interesting mechanical, electronic, optical and thermal conduction properties, which are promising for the design of novel nanodevices.

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

NASA Technical Reports Server (NTRS)

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

1987-01-01

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Provo, James L., E-mail: jlprovo@verizon.net

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 praseodymiummore » (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�

Texture and hydride orientation relationship of Zircaloy-4 fuel clad tube during its fabrication for pressurized heavy water reactors

NASA Astrophysics Data System (ADS)

Vaibhaw, Kumar; Rao, S. V. R.; Jha, S. K.; Saibaba, N.; Jayaraj, R. N.

2008-12-01

Zircaloy-4 material is used for cladding tube in pressurized heavy water reactors (PHWRs) of 220 MWe and 540 MWe capacity in India. These tubes are fabricated by using various combinations of thermo-mechanical processes to achieve desired mechanical and corrosion properties. Cladding tube develops crystallographic texture during its fabrication, which has significant influence on its in-reactor performance. Due to radiolytic decomposition of water Zircaloy-4 picks-up hydrogen. This hydrogen in excess of its maximum solubility in reactor operating condition (˜300 °C), precipitates as zirconium hydrides causing embrittlement of cladding tube. Hydride orientation in the radial direction of the tube limits the service life and lowers the fuel burn-up in reactor. The orientation of the hydride primarily depends on texture developed during fabrication. A correlation between hydride orientation ( F n) with the texture in the tube during its fabrication has been developed using a second order polynomial. The present work is aimed at quantification and correlation of texture evolved in Zircaloy-4 cladding tube using Kearn's f-parameter during its fabrication process.

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

PubMed

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

2011-08-10

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

Mechanical properties of zirconium alloys and zirconium hydrides predicted from density functional perturbation theory

DOE PAGES

Weck, Philippe F.; Kim, Eunja; Tikare, Veena; ...

2015-10-13

Here, the elastic properties and mechanical stability of zirconium alloys and zirconium hydrides have been investigated within the framework of density functional perturbation theory. Results show that the lowest-energy cubic Pn-3m with combining macron]m polymorph of δ-ZrH 1.5 does not satisfy all the Born requirements for mechanical stability, unlike its nearly degenerate tetragonal P4 2/ mcm polymorph. Elastic moduli predicted with the Voigt–Reuss–Hill approximations suggest that mechanical stability of α-Zr, Zr-alloy and Zr-hydride polycrystalline aggregates is limited by the shear modulus. According to both Pugh's and Poisson's ratios, α-Zr, Zr-alloy and Zr-hydride polycrystalline aggregates can be considered ductile. The Debyemore » temperatures predicted for γ-ZrH, δ-ZrH 1.5 and ε-ZrH 2 are θ D = 299.7, 415.6 and 356.9 K, respectively, while θ D = 273.6, 284.2, 264.1 and 257.1 K for the α-Zr, Zry-4, ZIRLO and M5 matrices, i.e. suggesting that Zry-4 possesses the highest micro-hardness among Zr matrices.« less

Method and composition in which metal hydride particles are embedded in a silica network

DOEpatents

Heung, Leung K.

1999-01-01

A silica embedded metal hydride composition and a method for making such a composition. The composition is made via the following process: A quantity of fumed silica is blended with water to make a paste. After adding metal hydride particles, the paste is dried to form a solid. According to one embodiment of the invention, the solid is ground into granules for use of the product in hydrogen storage. Alternatively, the paste can be molded into plates or cylinders and then dried for use of the product as a hydrogen filter. Where mechanical strength is required, the paste can be impregnated in a porous substrate or wire network.

Method to predict relative hydriding within a group of zirconium alloys under nuclear irradiation

DOEpatents

Johnson, A.B. Jr.; Levy, I.S.; Trimble, D.J.; Lanning, D.D.; Gerber, F.S.

1990-04-10

An out-of-reactor method for screening to predict relative in-reactor hydriding behavior of zirconium-based materials is disclosed. Samples of zirconium-based materials having different compositions and/or fabrication methods are autoclaved in a relatively concentrated (0.3 to 1.0M) aqueous lithium hydroxide solution at constant temperatures within the water reactor coolant temperature range (280 to 316 C). Samples tested by this out-of-reactor procedure, when compared on the basis of the ratio of hydrogen weight gain to oxide weight gain, accurately predict the relative rate of hydriding for the same materials when subject to in-reactor (irradiated) corrosion. 1 figure.

Tryptophan 80 and leucine 143 are critical for the hydride transfer step of thymidylate synthase by controlling active site access.

PubMed

Fritz, Timothy A; Liu, Lu; Finer-Moore, Janet S; Stroud, Robert M

2002-06-04

Mutant forms of thymidylate synthase (TS) with substitutions at the conserved active site residue, Trp 80, are deficient in the hydride transfer step of the TS reaction. These mutants produce a beta-mercaptoethanol (beta-ME) adduct of the 2'-deoxyuridine-5'-monophosphate (dUMP) exocyclic methylene intermediate. Trp 80 has been proposed to assist hydride transfer by stabilizing a 5,6,7,8-tetrahydrofolate (THF) radical cation intermediate [Barrett, J. E., Lucero, C. M., and Schultz, P. G. (1999) J. Am. Chem. Soc. 121, 7965-7966.] formed after THF changes its binding from the cofactor pocket to a putative alternate site. To understand the molecular basis of hydride transfer deficiency in a mutant in which Trp 80 was changed to Gly, we determined the X-ray structures of this mutant Escherichia coli TS complexed with dUMP and the folate analogue 10-propargyl-5,8-dideazafolate (CB3717) and of the wild-type enzyme complexed with dUMP and THF. The mutant enzyme has a cavity in the active site continuous with bulk solvent. This cavity, sealed from bulk solvent in wild-type TS by Leu 143, would allow nucleophilic attack of beta-ME on the dUMP C5 exocyclic methylene. The structure of the wild-type enzyme/dUMP/THF complex shows that THF is bound in the cofactor binding pocket and is well positioned to transfer hydride to the dUMP exocyclic methylene. Together, these results suggest that THF does not reorient during hydride transfer and indicate that the role of Trp 80 may be to orient Leu 143 to shield the active site from bulk solvent and to optimally position the cofactor for hydride transfer.

Refinements in an Mg/MgH2/H2O-Based Hydrogen Generator

NASA Technical Reports Server (NTRS)

Kindler, Andrew; Huang, Yuhong

2010-01-01

Some refinements have been conceived for a proposed apparatus that would generate hydrogen (for use in a fuel cell) by means of chemical reactions among magnesium, magnesium hydride, and steam. The refinements lie in tailoring spatial and temporal distributions of steam and liquid water so as to obtain greater overall energy-storage or energy-generation efficiency than would otherwise be possible. A description of the prior art is prerequisite to a meaningful description of the present refinements. The hydrogen-generating apparatus in question is one of two versions of what was called the "advanced hydrogen generator" in "Fuel-Cell Power Systems Incorporating Mg-Based H2 Generators" (NPO-43554), NASA Tech Briefs, Vol. 33, No. 1 (January 2009), page 52. To recapitulate: The apparatus would include a reactor vessel that would be initially charged with magnesium hydride. The apparatus would exploit two reactions: The endothermic decomposition reaction MgH2-->Mg + H2, which occurs at a temperature greater than or equal to 300 C, and The exothermic oxidation reaction MgH2 + H2O MgO + 2H2, which occurs at a temperature greater than or equal to 330 C.

An automatic granular structure generation and finite element analysis of heterogeneous semi-solid materials

NASA Astrophysics Data System (ADS)

Sharifi, Hamid; Larouche, Daniel

2015-09-01

The quality of cast metal products depends on the capacity of the semi-solid metal to sustain the stresses generated during the casting. Predicting the evolution of these stresses with accuracy in the solidification interval should be highly helpful to avoid the formation of defects like hot tearing. This task is however very difficult because of the heterogeneous nature of the material. In this paper, we propose to evaluate the mechanical behaviour of a metal during solidification using a mesh generation technique of the heterogeneous semi-solid material for a finite element analysis at the microscopic level. This task is done on a two-dimensional (2D) domain in which the granular structure of the solid phase is generated surrounded by an intergranular and interdendritc liquid phase. Some basic solid grains are first constructed and projected in the 2D domain with random orientations and scale factors. Depending on their orientation, the basic grains are combined to produce larger grains or separated by a liquid film. Different basic grain shapes can produce different granular structures of the mushy zone. As a result, using this automatic grain generation procedure, we can investigate the effect of grain shapes and sizes on the thermo-mechanical behaviour of the semi-solid material. The granular models are automatically converted to the finite element meshes. The solid grains and the liquid phase are meshed properly using quadrilateral elements. This method has been used to simulate the microstructure of a binary aluminium-copper alloy (Al-5.8 wt% Cu) when the fraction solid is 0.92. Using the finite element method and the Mie-Grüneisen equation of state for the liquid phase, the transient mechanical behaviour of the mushy zone under tensile loading has been investigated. The stress distribution and the bridges, which are formed during the tensile loading, have been detected.

Importance of a serine proximal to the C(4a) and N(5) flavin atoms for hydride transfer in choline oxidase.

PubMed

Yuan, Hongling; Gadda, Giovanni

2011-02-08

Choline oxidase catalyzes the flavin-dependent, two-step oxidation of choline to glycine betaine with the formation of an aldehyde intermediate. In the first oxidation reaction, the alcohol substrate is initially activated to its alkoxide via proton abstraction. The substrate is oxidized via transfer of a hydride from the alkoxide α-carbon to the N(5) atom of the enzyme-bound flavin. In the wild-type enzyme, proton and hydride transfers are mechanistically and kinetically uncoupled. In this study, we have mutagenized an active site serine proximal to the C(4a) and N(5) atoms of the flavin and investigated the reactions of proton and hydride transfers by using substrate and solvent kinetic isotope effects. Replacement of Ser101 with threonine, alanine, cysteine, or valine resulted in biphasic traces in anaerobic reductions of the flavin with choline investigated in a stopped-flow spectrophotometer. Kinetic isotope effects established that the kinetic phases correspond to the proton and hydride transfer reactions catalyzed by the enzyme. Upon removal of Ser101, there is an at least 15-fold decrease in the rate constants for proton abstraction, irrespective of whether threonine, alanine, valine, or cysteine is present in the mutant enzyme. A logarithmic decrease spanning 4 orders of magnitude is seen in the rate constants for hydride transfer with increasing hydrophobicity of the side chain at position 101. This study shows that the hydrophilic character of a serine residue proximal to the C(4a) and N(5) flavin atoms is important for efficient hydride transfer.

Predicted energy densitites for nickel-hydrogen and silver-hydrogen cells embodying metallic hydrides for hydrogen storage

NASA Technical Reports Server (NTRS)

Easter, R. W.

1974-01-01

Simplified design concepts were used to estimate gravimetric and volumetric energy densities for metal hydrogen battery cells for assessing the characteristics of cells containing metal hydrides as compared to gaseous storage cells, and for comparing nickel cathode and silver cathode systems. The silver cathode was found to yield superior energy densities in all cases considered. The inclusion of hydride forming materials yields cells with very high volumetric energy densities that also retain gravimetric energy densities nearly as high as those of gaseous storage cells.

Complex hydrides as room-temperature solid electrolytes for rechargeable batteries

NASA Astrophysics Data System (ADS)

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.

Superconductivity above the lowest Earth temperature in pressurized sulfur hydride

NASA Astrophysics Data System (ADS)

Bianconi, Antonio; Jarlborg, Thomas

2015-11-01

A recent experiment has shown a macroscopic quantum coherent condensate at 203 K, about 19 degrees above the coldest temperature recorded on the Earth surface, 184 K (-89.2 ^\\circ \\text{C}, -128.6 ^\\circ \\text{F}) in pressurized sulfur hydride. This discovery is relevant not only in material science and condensed matter but also in other fields ranging from quantum computing to quantum physics of living matter. It has given the start to a gold rush looking for other macroscopic quantum coherent condensates in hydrides at the temperature range of living matter 200c <400 \\text{K} . We present here a review of the experimental results and the theoretical works and we discuss the Fermiology of \\text{H}3\\text{S} focusing on Lifshitz transitions as a function of pressure. We discuss the possible role of the shape resonance near a neck disrupting Lifshitz transition, in the Bianconi-Perali-Valletta (BPV) theory, for rising the critical temperature in a multigap superconductor, as the Feshbach resonance rises the critical temperature in Fermionic ultracold gases.

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

PubMed

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

2016-03-30

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

The unexpected mechanism underlying the high-valent mono-oxo-rhenium(V) hydride catalyzed hydrosilylation of C=N functionalities: insights from a DFT study.

PubMed

Wang, Jiandi; Wang, Wenmin; Huang, Liangfang; Yang, Xiaodi; Wei, Haiyan

2015-04-07

In this study, we theoretically investigated the mechanism underlying the high-valent mono-oxo-rhenium(V) hydride Re(O)HCl2(PPh3)2 (1) catalyzed hydrosilylation of C=N functionalities. Our results suggest that an ionic S(N)2-Si outer-sphere pathway involving the heterolytic cleavage of the Si-H bond competes with the hydride pathway involving the C=N bond inserted into the Re-H bond for the rhenium hydride (1) catalyzed hydrosilylation of the less steric C=N functionalities (phenylmethanimine, PhCH=NH, and N-phenylbenzylideneimine, PhCH=NPh). The rate-determining free-energy barriers for the ionic outer-sphere pathway are calculated to be ∼28.1 and 27.6 kcal mol(-1), respectively. These values are slightly more favorable than those obtained for the hydride pathway (by ∼1-3 kcal mol(-1)), whereas for the large steric C=N functionality of N,1,1-tri(phenyl)methanimine (PhCPh=NPh), the ionic outer-sphere pathway (33.1 kcal mol(-1)) is more favorable than the hydride pathway by as much as 11.5 kcal mol(-1). Along the ionic outer-sphere pathway, neither the multiply bonded oxo ligand nor the inherent hydride moiety participate in the activation of the Si-H bond. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

METHOD FOR PRODUCING ISOTOPIC METHANES FROM LITHIUM CARBONATE AND LITHIUM HYDRIDE

DOEpatents

Frazer, J.W.

1959-10-27

A process is descrlbed for the production of methane and for the production of methane containing isotopes of hydrogen and/or carbon. Finely divided lithium hydrlde and litldum carbonate reactants are mixed in intimate contact and subsequently compacted under pressures of from 5000 to 60,000 psl. The compacted lithium hydride and lithium carbenate reactunts are dispised in a gas collecting apparatus. Subsequently, the compact is heated to a temperature in the range 350 to 400 deg C whereupon a solid-solid reaction takes place and gaseous methane is evolved. The evolved methane is contaminated with gaseous hydrogen and a very small amount of CO/sub 2/; however, the desired methane product is separated from sald impurities by well known chemical processes, e.g., condensation in a cold trap. The product methane contalns isotopes of carbon and hydrogen, the Isotopic composition being determined by the carbon isotopes originally present In the lithium carbonate and the hydrogen isotopes originally present in the lithium hydride.

High Resolution Neutron Radiography and Tomography of Hydrided Zircaloy-4 Cladding Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Tyler S; Bilheux, Hassina Z; Ray, Holly B

2015-01-01

Neutron radiography for hydrogen analysis was performed with several Zircaloy-4 cladding samples with controlled hydrogen concentrations up to 1100 ppm. Hydrogen charging was performed in a process tube that was heated to facilitate hydrogen absorption by the metal. A correlation between the hydrogen concentration in the hydrided tubes and the neutron intensity was established, by which hydrogen content can be determined precisely in a small area (55 m x 55 m). Radiography analysis was also performed to evaluate the heating rate and its correlation with the hydrogen distribution through hydrided materials. In addition to radiography analysis, tomography experiments were performedmore » on Zircaloy-4 tube samples to study the local hydrogen distribution. Through tomography analysis a 3D reconstruction of the tube was evaluated in which an uneven hydrogen distribution in the circumferential direction can be observed.« less

Diffractive elements for generating microscale laser beam patterns: a Y2K problem

NASA Astrophysics Data System (ADS)

Teiwes, Stephan; Krueger, Sven; Wernicke, Guenther K.; Ferstl, Margit

2000-03-01

Lasers are widely used in industrial fabrication for engraving, cutting and many other purposes. However, material processing at very small scales is still a matter of concern. Advances in diffractive optics could provide for laser systems that could be used for engraving or cutting of micro-scale patterns at high speeds. In our paper we focus on the design of diffractive elements which can be used for this special application. It is a common desire in material processing to apply 'discrete' as well as 'continuous' beam patterns. Especially, the latter case is difficult to handle as typical micro-scale patterns are characterized by bad band-limitation properties, and as speckles can easily occur in beam patterns. It is shown in this paper that a standard iterative design method usually fails to obtain diffractive elements that generate diffraction patterns with acceptable quality. Insights gained from an analysis of the design problems are used to optimize the iterative design method. We demonstrate applicability and success of our approach by the design of diffractive phase elements that generate a discrete and a continuous 'Y2K' pattern.

Simulation of high temperature thermal energy storage system based on coupled metal hydrides for solar driven steam power plants

DOE PAGES

d'Entremont, Anna; Corgnale, Claudio; Hardy, Bruce; ...

2018-01-11

Concentrating solar power plants can achieve low cost and efficient renewable electricity production if equipped with adequate thermal energy storage systems. Metal hydride based thermal energy storage systems are appealing candidates due to their demonstrated potential for very high volumetric energy densities, high exergetic efficiencies, and low costs. The feasibility and performance of a thermal energy storage system based on NaMgH 2F hydride paired with TiCr 1.6Mn 0.2 is examined, discussing its integration with a solar-driven ultra-supercritical steam power plant. The simulated storage system is based on a laboratory-scale experimental apparatus. It is analyzed using a detailed transport model accountingmore » for the thermochemical hydrogen absorption and desorption reactions, including kinetics expressions adequate for the current metal hydride system. The results show that the proposed metal hydride pair can suitably be integrated with a high temperature steam power plant. The thermal energy storage system achieves output energy densities of 226 kWh/m 3, 9 times the DOE SunShot target, with moderate temperature and pressure swings. Also, simulations indicate that there is significant scope for performance improvement via heat-transfer enhancement strategies.« less

Simulation of high temperature thermal energy storage system based on coupled metal hydrides for solar driven steam power plants

DOE Office of Scientific and Technical Information (OSTI.GOV)

d'Entremont, Anna; Corgnale, Claudio; Hardy, Bruce

Concentrating solar power plants can achieve low cost and efficient renewable electricity production if equipped with adequate thermal energy storage systems. Metal hydride based thermal energy storage systems are appealing candidates due to their demonstrated potential for very high volumetric energy densities, high exergetic efficiencies, and low costs. The feasibility and performance of a thermal energy storage system based on NaMgH 2F hydride paired with TiCr 1.6Mn 0.2 is examined, discussing its integration with a solar-driven ultra-supercritical steam power plant. The simulated storage system is based on a laboratory-scale experimental apparatus. It is analyzed using a detailed transport model accountingmore » for the thermochemical hydrogen absorption and desorption reactions, including kinetics expressions adequate for the current metal hydride system. The results show that the proposed metal hydride pair can suitably be integrated with a high temperature steam power plant. The thermal energy storage system achieves output energy densities of 226 kWh/m 3, 9 times the DOE SunShot target, with moderate temperature and pressure swings. Also, simulations indicate that there is significant scope for performance improvement via heat-transfer enhancement strategies.« less

In-Bed Accountability Development for a Passively Cooled, Electrically Heated Hydride (PACE) Bed

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klein, J.E.

A nominal 1500 STP-L PAssively Cooled, Electrically heated hydride (PACE) Bed has been developed for implementation into a new Savannah River Site tritium project. The 1.2 meter (four-foot) long process vessel contains on internal 'U-tube' for tritium In-Bed Accountability (IBA) measurements. IBA will be performed on six, 12.6 kg production metal hydride storage beds.IBA tests were done on a prototype bed using electric heaters to simulate the radiolytic decay of tritium. Tests had gas flows from 10 to 100 SLPM through the U-tube or 100 SLPM through the bed's vacuum jacket. IBA inventory measurement errors at the 95% confidence levelmore » were calculated using the correlation of IBA gas temperature rise, or (hydride) bed temperature rise above ambient temperature, versus simulated tritium inventory.Prototype bed IBA inventory errors at 100 SLPM were the largest for gas flows through the vacuum jacket: 15.2 grams for the bed temperature rise and 11.5 grams for the gas temperature rise. For a 100 SLPM U-tube flow, the inventory error was 2.5 grams using bed temperature rise and 1.6 grams using gas temperature rise. For 50 to 100 SLPM U-tube flows, the IBA gas temperature rise inventory errors were nominally one to two grams that increased above four grams for flows less than 50 SLPM. For 50 to 100 SLPM U-tube flows, the IBA bed temperature rise inventory errors were greater than the gas temperature rise errors, but similar errors were found for both methods at gas flows of 20, 30, and 40 SLPM.Electric heater IBA tests were done for six production hydride beds using a 45 SLPM U-tube gas flow. Of the duplicate runs performed on these beds, five of the six beds produced IBA inventory errors of approximately three grams: consistent with results obtained in the laboratory prototype tests.« less

In-Bed Accountability Development for a Passively Cooled, Electrically Heated Hydride (PACE) Bed

DOE Office of Scientific and Technical Information (OSTI.GOV)

KLEIN, JAMES

A nominal 1500 STP-L PAssively Cooled, Electrically heated hydride (PACE) Bed has been developed for implementation into a new Savannah River Site tritium project. The 1.2 meter (four-foot) long process vessel contains an internal ''U-tube'' for tritium In-Bed Accountability (IBA) measurements. IBA will be performed on six, 12.6 kg production metal hydride storage beds. IBA tests were done on a prototype bed using electric heaters to simulate the radiolytic decay of tritium. Tests had gas flows from 10 to 100 SLPM through the U-tube or 100 SLPM through the bed's vacuum jacket. IBA inventory measurement errors at the 95 percentmore » confidence level were calculated using the correlation of IBA gas temperature rise, or (hydride) bed temperature rise above ambient temperature, versus simulated tritium inventory. Prototype bed IBA inventory errors at 100 SLPM were the largest for gas flows through the vacuum jacket: 15.2 grams for the bed temperature rise and 11.5 grams for the gas temperature rise. For a 100 SLPM U-tube flow, the inventory error was 2.5 grams using bed temperature rise and 1.6 grams using gas temperature rise. For 50 to 100 SLPM U-tube flows, the IBA gas temperature rise inventory errors were nominally one to two grams that increased above four grams for flows less than 50 SLPM. For 50 to 100 SLPM U-tube flows, the IBA bed temperature rise inventory errors were greater than the gas temperature rise errors, but similar errors were found for both methods at gas flows of 20, 30, and 40 SLPM. Electric heater IBA tests were done for six production hydride beds using a 45 SLPM U-tube gas flow. Of the duplicate runs performed on these beds, five of the six beds produced IBA inventory errors of approximately three grams: consistent with results obtained in the laboratory prototype tests.« less

Automotive dual-mode hydrogen generation system

NASA Astrophysics Data System (ADS)

Kelly, D. A.

The automotive dual mode hydrogen generation system is advocated as a supplementary hydrogen fuel means along with the current metallic hydride hydrogen storage method for vehicles. This system consists of utilizing conventional electrolysis cells with the low voltage dc electrical power supplied by two electrical generating sources within the vehicle. Since the automobile engine exhaust manifold(s) are presently an untapped useful source of thermal energy, they can be employed as the heat source for a simple heat engine/generator arrangement. The second, and minor electrical generating means consists of multiple, miniature air disk generators which are mounted directly under the vehicle's hood and at other convenient locations within the engine compartment. The air disk generators are revolved at a speed which is proportionate to the vehicles forward speed and do not impose a drag on the vehicles motion.

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

PubMed

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

2016-04-27

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

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

PubMed

Deegan, Meaghan M; Peters, Jonas C

2017-02-22

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

2007-08-01

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

Characterization of spent nickel-metal hydride batteries and a preliminary economic evaluation of the recovery processes.

PubMed

Lin, Sheng-Lun; Huang, Kuo-Lin; Wang, I-Ching; Chou, I-Cheng; Kuo, Yi-Ming; Hung, Chung-Hsien; Lin, Chitsan

2016-03-01

Valuable metal materials can be recovered from spent nickel-metal hydride (NiMH) batteries. However, little attention has been paid to the metal compositions of individual components of NiMH batteries, although this is important for the selection of the appropriate recycling process. In this study, NiMH batteries were manually disassembled to identify the components and to characterize the metals in each of these. A preliminary economic analysis was also conducted to evaluate the recovery of valuable metals from spent NiMH batteries using thermal melting versus simple mechanical separation. The results of this study show that metallic components account for more than 60% of battery weight. The contents of Ni, Fe, Co, and rare earth elements (REEs) (i.e., valuable metals of interest for recovery) in a single battery were 17.9%, 15.4%, 4.41%, and 17.3%, respectively. Most of the Fe was in the battery components of the steel cathode collector, cathode cap, and anode metal grid, while Ni (>90%) and Co (>90%) were mainly in the electrode active materials (anode and cathode metal powders). About 1.88 g of REEs (Ce, La, and Y) could be obtained from one spent NiMH battery. The estimated profits from recovering valuable metals from spent NiMH batteries by using thermal melting and mechanical processes are 2,329 and 2,531 USD/ton, respectively, when including a subsidy of 1,710 USD/ton. The findings of this study are very useful for further research related to technical and economic evaluations of the recovery of valuable metals from spent NiMH batteries. The spent nickel-metal hydride (NiMH) batteries were manually disassembled and their components were identified. The metals account for more than 60% of battery weight, when Ni, Fe, Co, and rare earth elements (REEs) were 17.9%, 15.4%, 4.41%, and 17.3%, respectively, in a single battery. The estimated profits of recovering valuable metals from NiMH batteries by using thermal melting and mechanical processing are 2,329 and

Modeling of a thermal energy storage system based on coupled metal hydrides (magnesium iron – sodium alanate) for concentrating solar power plants

DOE PAGES

d'Entremont, A.; Corgnale, C.; Sulic, M.; ...

2017-08-31

Concentrating solar power plants represent low cost and efficient solutions for renewable electricity production only if adequate thermal energy storage systems are included. Metal hydride thermal energy storage systems have demonstrated the potential to achieve very high volumetric energy densities, high exergetic efficiencies, and low costs. The current work analyzes the technical feasibility and the performance of a storage system based on the high temperature Mg 2FeH 6 hydride coupled with the low temperature Na 3AlH 6 hydride. To accomplish this, a detailed transport model has been set up and the coupled metal hydride system has been simulated based onmore » a laboratory scale experimental configuration. Proper kinetics expressions have been developed and included in the model to replicate the absorption and desorption process in the high temperature and low temperature hydride materials. The system showed adequate hydrogen transfer between the two metal hydrides, with almost complete charging and discharging, during both thermal energy storage and thermal energy release. The system operating temperatures varied from 450°C to 500°C, with hydrogen pressures between 30 bar and 70 bar. This makes the thermal energy storage system a suitable candidate for pairing with a solar driven steam power plant. The model results, obtained for the selected experimental configuration, showed an actual thermal energy storage system volumetric energy density of about 132 kWh/m 3, which is more than 5 times the U.S. Department of Energy SunShot target (25 kWh/m 3).« less

Modeling of a thermal energy storage system based on coupled metal hydrides (magnesium iron – sodium alanate) for concentrating solar power plants

DOE Office of Scientific and Technical Information (OSTI.GOV)

d'Entremont, A.; Corgnale, C.; Sulic, M.

Concentrating solar power plants represent low cost and efficient solutions for renewable electricity production only if adequate thermal energy storage systems are included. Metal hydride thermal energy storage systems have demonstrated the potential to achieve very high volumetric energy densities, high exergetic efficiencies, and low costs. The current work analyzes the technical feasibility and the performance of a storage system based on the high temperature Mg 2FeH 6 hydride coupled with the low temperature Na 3AlH 6 hydride. To accomplish this, a detailed transport model has been set up and the coupled metal hydride system has been simulated based onmore » a laboratory scale experimental configuration. Proper kinetics expressions have been developed and included in the model to replicate the absorption and desorption process in the high temperature and low temperature hydride materials. The system showed adequate hydrogen transfer between the two metal hydrides, with almost complete charging and discharging, during both thermal energy storage and thermal energy release. The system operating temperatures varied from 450°C to 500°C, with hydrogen pressures between 30 bar and 70 bar. This makes the thermal energy storage system a suitable candidate for pairing with a solar driven steam power plant. The model results, obtained for the selected experimental configuration, showed an actual thermal energy storage system volumetric energy density of about 132 kWh/m 3, which is more than 5 times the U.S. Department of Energy SunShot target (25 kWh/m 3).« less

Equivalent circuit parameters of nickel/metal hydride batteries from sparse impedance measurements

NASA Astrophysics Data System (ADS)

Nelatury, Sudarshan Rao; Singh, Pritpal

In a recent communication, a method for extracting the equivalent circuit parameters of a lead acid battery from sparse (only three) impedance spectroscopy observations at three different frequencies was proposed. It was based on an equivalent circuit consisting of a bulk resistance, a reaction resistance and a constant phase element (CPE). Such a circuit is a very appropriate model of a lead-acid cell at high state of charge (SOC). This paper is a sequel to it and presents an application of it in case of nickel/metal hydride (Ni/MH) batteries, which also at high SOC are represented by the same circuit configuration. But when the SOC of a Ni/MH battery under interrogation goes low, The EIS curve has a positive slope at the low frequency end and our technique yields complex values for the otherwise real circuit parameters, suggesting the need for additional elements in the equivalent circuit and a definite relationship between parameter consistency and SOC. To improvise the previous algorithm, in order that it works reasonably well at both high and low SOCs, we propose three more measurements—two at very low frequencies to include the Warburg response and one at a high frequency to model the series inductance, in addition to the three in the mid frequency band—totally six measurements. In most of the today's instrumentation, it is the user who should choose the circuit configuration and the number of frequencies where impedance should be measured and the accompanying software performs data fitting by complex nonlinear least squares. The proposed method has built into it an SOC-based decision-making capability—both to choose the circuit configuration and to estimate the values of the circuit elements.

Bipolar Nickel-Metal Hydride Battery Development Project

NASA Technical Reports Server (NTRS)

Cole, John H.

1999-01-01

This paper reviews the development of the Electro Energy, Inc.'s bipolar nickel metal hydride battery. The advantages of the design are that each cell is individually sealed, and that there are no external cell terminals, no electrode current collectors, it is compatible with plastic bonded electrodes, adaptable to heat transfer fins, scalable to large area, capacity and high voltage. The design will allow for automated flexible manufacturing, improved energy and power density and lower cost. The development and testing of the battery's component are described. Graphic presentation of the results of many of the tests are included.

INVESTIGATION OF ARSINE-GENERATING REACTIONS USING DEUTERIUM-LABELED REAGENTS AND MASS SPECTROMETRY

EPA Science Inventory

Mass spectrometry was used to detect transfer of deuterium from labeled reagents to arsines following hydride-generation reactions. The arsine gases liberated from the reactions of arsenite, arsenate, methylarsonic acid, and dimethylarsinic acid with HC1 and NaBD4 in H2O, or with...

Rh-Catalyzed Intermolecular Reactions of α-Alkyl-α-Diazo Carbonyl Compounds with Selectivity over β-Hydride Migration.

PubMed

DeAngelis, Andrew; Panish, Robert; Fox, Joseph M

2016-01-19

Rh-carbenes derived from α-diazocarbonyl compounds have found broad utility across a remarkable range of reactivity, including cyclopropanation, cyclopropenation, C-H insertions, heteroatom-hydrogen insertions, and ylide forming reactions. However, in contrast to α-aryl or α-vinyl-α-diazocarbonyl compounds, the utility of α-alkyl-α-diazocarbonyl compounds had been moderated by the propensity of such compounds to undergo intramolecular β-hydride migration to give alkene products. Especially challenging had been intermolecular reactions involving α-alkyl-α-diazocarbonyl compounds. This Account discusses the historical context and prior limitations of Rh-catalyzed reactions involving α-alkyl-α-diazocarbonyl compounds. Early studies demonstrated that ligand and temperature effects could influence chemoselectivity over β-hydride migration. However, effects were modest and conflicting conclusions had been drawn about the influence of sterically demanding ligands on β-hydride migration. More recent advances have led to a more detailed understanding of the reaction conditions that can promote intermolecular reactivity in preference to β-hydride migration. In particular, the use of bulky carboxylate ligands and low reaction temperatures have been key to enabling intermolecular cyclopropenation, cyclopropanation, carbonyl ylide formation/dipolar cycloaddition, indole C-H functionalization, and intramolecular bicyclobutanation with high chemoselectivity over β-hydride migration. Cyclic α-diazocarbonyl compounds have been shown to be particularly resilient toward β-hydride migration and are the first class of compounds that can engage in intermolecular reactivity in the presence of tertiary β-hydrogens. DFT calculations were used to propose that for cyclic α-diazocarbonyl compounds, ring constraints relieve steric interaction for intermolecular reactions and thereby accelerate the rate of intermolecular reactivity relative to intramolecular β-hydride

Combined passive bearing element/generator motor

DOEpatents

Post, Richard F.

2000-01-01

An electric machine includes a cylindrical rotor made up of an array of permanent magnets that provide a N-pole magnetic field of even order (where N=4, 6, 8, etc.). This array of permanent magnets has bars of identical permanent magnets made of dipole elements where the bars are assembled in a circle. A stator inserted down the axis of the dipole field is made of two sets of windings that are electrically orthogonal to each other, where one set of windings provides stabilization of the stator and the other set of windings couples to the array of permanent magnets and acts as the windings of a generator/motor. The rotor and the stator are horizontally disposed, and the rotor is on the outside of said stator. The electric machine may also include two rings of ferromagnetic material. One of these rings would be located at each end of the rotor. Two levitator pole assemblies are attached to a support member that is external to the electric machine. These levitator pole assemblies interact attractively with the rings of ferromagnetic material to produce a levitating force upon the rotor.

Exceptional Lithium Storage in a Co(OH) 2 Anode: Hydride Formation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Hyunchul; Choi, Woon Ih; Jang, Yoonjung

Current lithium ion battery technology is tied in with conventional reaction mechanisms such as insertion, conversion, and alloying reactions even though most future applications like EVs demand much higher energy densities than current ones. Exploring the exceptional reaction mechanism and related electrode materials can be critical for pushing current battery technology to a next level. Here, we introduce an exceptional reaction with a Co(OH)(2) material which exhibits an initial charge capacity of 1112 mAh g(-1), about twice its theoretical value based on known conventional conversion reaction, and retains its first cycle capacity after 30 cycles. The combined results of synchrotronmore » X-ray diffraction and X-ray absorption spectroscopy indicate that nanosized Co metal particles and LiOH are generated by conversion reaction at high voltages, and CoxHy, Li2O, and LiH are subsequently formed by hydride reaction between Co metal, LiOH, and other lithium species at low voltages, resulting in a anomalously high capacity beyond the theoretical capacity of Co(OH)(2). This is further corroborated by AIMD simulations, localized STEM, and XPS. These findings will provide not only further understanding of exceptional lithium storage of recent nanostructured materials but also valuable guidance to develop advanced electrode materials with high energy density for next-generation batteries.« less

Direct conversion of hydride- to siloxane-terminated silicon quantum dots

DOE PAGES

Anderson, Ryan T.; Zang, Xiaoning; Fernando, Roshan; ...

2016-10-20

Here, peripheral surface functionalization of hydride-terminated silicon quantum dots (SiQD) is necessary in order to minimize their oxidation/aggregation and allow for solution processability. Historically thermal hydrosilylation addition of alkenes and alkynes across the Si-H surface to form Si-C bonds has been the primary method to achieve this. Here we demonstrate a mild alternative approach to functionalize hydride-terminated SiQDs using bulky silanols in the presence of free-radical initiators to form stable siloxane (~Si-O-SiR 3) surfaces with hydrogen gas as a byproduct. This offers an alternative to existing methods of forming siloxane surfaces that require corrosive Si-Cl based chemistry with HCl byproducts.more » A 52 nm blue shift in the photoluminescent spectra of siloxane versus alkyl-functionalized SiQDs is observed that we explain using computational theory. Model compound synthesis of silane and silsesquioxane analogues is used to optimize surface chemistry and elucidate reaction mechanisms. Thorough characterization on the extent of siloxane surface coverage is provided using FTIR and XPS. As a result, TEM is used to demonstrate SiQD size and integrity after surface chemistry and product isolation.« less

Trace determination of Hg together with As, Sb, Se by miniaturized optical emission spectrometry integrated with chemical vapor generation and capacitively coupled argon microwave miniplasma discharge

NASA Astrophysics Data System (ADS)

Matusiewicz, Henryk; Ślachciński, Mariusz

2017-07-01

A miniaturized optical emission spectrometer (OES) with capacitively coupled argon microwave microplasma (μCMP) as and excitation source and chemical vapor generation (CVG) for sample introduction was constructed for the determination of trace Hg, As, Sb and Se. The applied method enabled simultaneous determination of hydride-forming elements (As, Sb, Se) and volatile Hg. Mercury cold vapor and the hydride volatile species of As, Sb and Se were generated when standard or sample solutions were separated from the liquid phase for transport to the capacitively coupled microwave microplasma and detection of their atomic emission. A univariate approach and the simplex optimization procedure were used to achieve optimized conditions and derive analytical figures of merit. The experimental concentration detection limits (LODs) for simultaneous determination, calculated as the concentration giving a signal equal to three times of the standard deviation of the blank (LOD, 3σblank criterion, peak height) were 3.0, 1.4, 1.5 and 3.8 ng mL- 1 for Hg, As, Sb and Se, respectively. The method was validated by the analysis of three Certified Reference Materials (NIST 2711, NRCC DOLT-2, NIST 1643e) of different matrix composition and by the standard addition technique. The method offers relatively good precision (RSD ranged from 5% to 8%) for microsampling (200 μL) analysis. The measured of contents of elements in certified reference materials were in good agreement with the certified values (Hg 1.99-6.25 μg g- 1, As 16.6-105 μg g- 1, Sb 19.4-56.88 μg g- 1, Se 1.52-11.68 μg g- 1), according to the Student t-test, for a confidence level of 95%.

In situ trapping of As, Sb and Se hydrides on nanometer-sized ceria-coated iron oxide-silica and slurry suspension introduction to ICP-OES.

PubMed

Dados, A; Kartsiouli, E; Chatzimitakos, Th; Papastephanou, C; Stalikas, C D

2014-12-01

A procedure is developed for the analysis of sub-μg L(-1) levels of arsenic, antimony and selenium after preconcentration of their hydrides. The study highlights the capability of an aqueous suspension of a nanometer-sized magnetic ceria, in the presence of iodide, to function as a sorbent for the in situ trapping and preconcentration of the hydrides of certain metalloids. After extraction, the material is magnetically separated from the trapping solution and analyzed. A slurry suspension sampling approach with inductively coupled plasma-optical emission spectrometry (ICP-OES) is employed for measurements, as the quantitative elution of the adsorbed metalloids is not feasible. The whole analytical procedure consists of five steps: (i) pre-reduction of As, Sb and Se, (ii) generation of the hydrides AsH3, SbH3 and SeH2, (iii) in situ collection in the trapping suspension of magnetic ceria, (iv) isolation of the particles by applying a magnetic field, and (v) measurement of As, Sb and Se concentrations using ICP-OES. Under the established experimental conditions, the efficiency of trapping accounted for 94 ± 2%, 89 ± 2% and 98 ± 3% for As, Sb and Se, respectively, signifying the effective implementation of the overall procedure. The applicability of the procedure has been demonstrated by analyzing tap and lake water and a reference material (soft drinking water). The obtained analytical figures of merit were satisfactory for the analysis of the above metalloids in natural waters by ICP-OES. Copyright © 2014 Elsevier B.V. All rights reserved.

Positronium hydride in hydrogen-laden thermochemically reduced MgO single crystals

NASA Astrophysics Data System (ADS)

Pareja, R.; de La Cruz, R. M.; Pedrosa, M. A.; González, R.; Chen, Y.

1990-04-01

Thermochemical reduction of hydrogen-laden MgO single crystals at T~2400 K results in a large concentration of both hydride (H-) ions and anion vacancies (>1024 m-3). Positron-lifetime experiments of these crystals provide evidence for bound positronium hydride states also referred to as [e+-H-] or PsH states. The presence of the anion vacancies was found to inhibit the formation of these states. After thermally annealing out these vacancies, such that H- concentration remains intact, two long-lived components appear in the lifetime spectrum. Furthermore, these two components correlate with the presence of the H-ions. These results suggest the existence of bound [e+-H-] states when positrons are trapped by the H- ions, and the subsequent formation of positronium (Ps) states by the dissociation of the [e+-H-] states. From the values of the intermediate lifetime component, a value of (570+/-50) ps is obtained for the lifetime of the PsH state located in an anion vacancy in MgO. The longest lifetime component ~(1-3) ns is attributed to pick-off annihilation of ortho-Ps states.

Detailed Modeling and Irreversible Transfer Process Analysis of a Multi-Element Thermoelectric Generator System

NASA Astrophysics Data System (ADS)

Xiao, Heng; Gou, Xiaolong; Yang, Suwen

2011-05-01

Thermoelectric (TE) power generation technology, due to its several advantages, is becoming a noteworthy research direction. Many researchers conduct their performance analysis and optimization of TE devices and related applications based on the generalized thermoelectric energy balance equations. These generalized TE equations involve the internal irreversibility of Joule heating inside the thermoelectric device and heat leakage through the thermoelectric couple leg. However, it is assumed that the thermoelectric generator (TEG) is thermally isolated from the surroundings except for the heat flows at the cold and hot junctions. Since the thermoelectric generator is a multi-element device in practice, being composed of many fundamental TE couple legs, the effect of heat transfer between the TE couple leg and the ambient environment is not negligible. In this paper, based on basic theories of thermoelectric power generation and thermal science, detailed modeling of a thermoelectric generator taking account of the phenomenon of energy loss from the TE couple leg is reported. The revised generalized thermoelectric energy balance equations considering the effect of heat transfer between the TE couple leg and the ambient environment have been derived. Furthermore, characteristics of a multi-element thermoelectric generator with irreversibility have been investigated on the basis of the new derived TE equations. In the present investigation, second-law-based thermodynamic analysis (exergy analysis) has been applied to the irreversible heat transfer process in particular. It is found that the existence of the irreversible heat convection process causes a large loss of heat exergy in the TEG system, and using thermoelectric generators for low-grade waste heat recovery has promising potential. The results of irreversibility analysis, especially irreversible effects on generator system performance, based on the system model established in detail have guiding significance for

Modeling of Gallium Nitride Hydride Vapor Phase Epitaxy

NASA Technical Reports Server (NTRS)

Meyyappan, Meyya; Arnold, James O. (Technical Monitor)

1997-01-01

A reactor model for the hydride vapor phase epitaxy of GaN is presented. The governing flow, energy, and species conservation equations are solved in two dimensions to examine the growth characteristics as a function of process variables and reactor geometry. The growth rate varies with GaCl composition but independent of NH3 and H2 flow rates. A change in carrier gas for Ga source from H2 to N2 affects the growth rate and uniformity for a fixed reactor configuration. The model predictions are in general agreement with observed experimental behavior.

Protein dynamics promote hydride tunnelling in substrate oxidation by aryl-alcohol oxidase.

PubMed

Carro, Juan; Martínez-Júlvez, Marta; Medina, Milagros; Martínez, Angel T; Ferreira, Patricia

2017-11-01

The temperature dependence of hydride transfer from the substrate to the N5 of the FAD cofactor during the reductive half-reaction of Pleurotus eryngii aryl-alcohol oxidase (AAO) is assessed here. Kinetic isotope effects on both the pre-steady state reduction of the enzyme and its steady-state kinetics, with differently deuterated substrates, suggest an environmentally-coupled quantum-mechanical tunnelling process. Moreover, those kinetic data, along with the crystallographic structure of the enzyme in complex with a substrate analogue, indicate that AAO shows a pre-organized active site that would only require the approaching of the hydride donor and acceptor for the tunnelled transfer to take place. Modification of the enzyme's active-site architecture by replacement of Tyr92, a residue establishing hydrophobic interactions with the substrate analogue in the crystal structure, in the Y92F, Y92L and Y92W variants resulted in different temperature dependence patterns that indicated a role of this residue in modulating the transfer reaction.

Impact of secondary generated minerals on toxic element immobilization for air pollution control fly ash of a municipal solid waste incinerator.

PubMed

Kitamura, Hiroki; Dahlan, Astryd Viandila; Tian, Yu; Shimaoka, Takayuki; Yamamoto, Takashi; Takahashi, Fumitake

2018-05-12

Impacts of secondary generated minerals on mineralogical and physical immobilization of toxic elements were investigated for chelate-treated air pollution control (APC) fly ash of a municipal solid waste incinerator. Scanning electron microscope (SEM) observation showed that ettringite was generated after the moistening treatment with/without chelate. Although ettringite can incorporate toxic elements into its structure, elemental analysis by energy dispersive X-ray could not find concentrated points of toxic elements in ettringite structure. This implies that mineralogical immobilization of toxic element by the encapsulation to ettringite structure seems to be limited. Physical immobilization was also investigated by SEM observation of the same APC fly ash particles before and after the moistening treatment. The transfer of soluble elements was inhibited only when insoluble minerals such as gypsum were generated and covered the surface of fly ash particles. Neoformed insoluble minerals prevented soluble elements from leaching and transfer. However, such physical immobilization seems to be limited because insoluble mineral formation with surface coverage was monitored only one time of more than 20 observations. Although uncertainty owing to limited samples with limited observations should be considered, this study concludes that mineralogical and physical immobilization of toxic elements by secondary minerals is limited although secondary minerals are always generated on the surface of APC fly ash particles during chelate treatment.

Interplay of water and reactive elements in oxidation of alumina-forming alloys.

PubMed

Mortazavi, N; Geers, C; Esmaily, M; Babic, V; Sattari, M; Lindgren, K; Malmberg, P; Jönsson, B; Halvarsson, M; Svensson, J E; Panas, I; Johansson, L G

2018-06-11

High-temperature alloys are crucial to many important technologies that underpin our civilization. All these materials rely on forming an external oxide layer (scale) for corrosion protection. Despite decades of research on oxide scale growth, many open questions remain, including the crucial role of the so-called reactive elements and water. Here, we reveal the hitherto unknown interplay between reactive elements and water during alumina scale growth, causing a metastable 'messy' nano-structured alumina layer to form. We propose that reactive-element-decorated, hydroxylated interfaces between alumina nanograins enable water to access an inner cathode in the bottom of the scale, at odds with the established scale growth scenario. As evidence, hydride-nanodomains and reactive element/hydrogen (deuterium) co-variation are observed in the alumina scale. The defect-rich alumina subsequently recrystallizes to form a protective scale. First-principles modelling is also performed to validate the RE effect. Our findings open up promising avenues in oxidation research and suggest ways to improve alloy properties.

Techniques for Unifying Disparate Elements in an EOS Instrument's Product Generation System Development Environment

NASA Technical Reports Server (NTRS)

Murray, Alex; Eng, Bjorn; Leff, Craig; Schwarz, Arnold

1997-01-01

In the development environment for ASTER level II product generation system, techniques have been incorporated to allow automated information sharing among all system elements, and to enable the use of sound software engineering techniques in the scripting languages.

Phase Equilibria, Crystal Structure and Hydriding/Dehydriding Mechanism of Nd4Mg80Ni8 Compound

PubMed Central

Luo, Qun; Gu, Qin-Fen; Zhang, Jie-Yu; Chen, Shuang-Lin; Chou, Kuo-Chih; Li, Qian

2015-01-01

In order to find out the optimal composition of novel Nd-Mg-Ni alloys for hydrogen storage, the isothermal section of Nd-Mg-Ni system at 400 °C is established by examining the equilibrated alloys. A new ternary compound Nd4Mg80Ni8 is discovered in the Mg-rich corner. It has the crystal structure of space group I41/amd with lattice parameters of a = b = 11.2743(1) Å and c = 15.9170(2) Å, characterized by the synchrotron powder X-ray diffraction (SR-PXRD). High-resolution transmission electron microscopy (HR-TEM) is used to investigate the microstructure of Nd4Mg80Ni8 and its hydrogen-induced microstructure evolution. The hydrogenation leads to Nd4Mg80Ni8 decomposing into NdH2.61-MgH2-Mg2NiH0.3 nanocomposites, where the high density phase boundaries provide a great deal of hydrogen atoms diffusion channels and nucleation sites of hydrides, which greatly enhances the hydriding/dehydriding (H/D) properties. The Nd4Mg80Ni8 exhibits a good cycle ability. The kinetic mechanisms of H/D reactions are studied by Real Physical Picture (RPP) model. The rate controlling steps are diffusion for hydriding reaction in the temperature range of 100 ~ 350 °C and surface penetration for dehydriding reaction at 291 ~ 347 °C. In-situ SR-PXRD results reveal the phase transformations of Mg to MgH2 and Mg2Ni to Mg2NiH4 as functions of hydrogen pressure and hydriding time. PMID:26471964

In situ electrochemical investigations of the kinetic and thermodynamic properties of nickel-metal hydride traction batteries

NASA Astrophysics Data System (ADS)

Yang, Xiao Guang; Liaw, Bor Yann

Although large ampere hour nickel-metal hydride (Ni-MH) traction batteries are in the stage of being commercialized for electric and hybrid vehicle applications, little is known about their performance characteristics. By using a standard Hg/HgO reference electrode in a commercial Ni-MH battery, we were able to conduct in situ measurements to determine both kinetic and thermodynamic properties of the system, including the characteristics of individual electrodes. Using the galvanostatic intermittent titration technique (GITT), we simultaneously and effectively determined the open-circuit voltage of the battery, the equilibrium electrode potentials, and the diffusion coefficient of proton and hydrogen in the nickel and metal hydride electrode, respectively, as a function of the states of charge (SOC). Using the current-step excitation technique, we found that the internal resistance of the battery primarily comes from the metal hydride electrode, which is greater by one order of magnitude than that of the Ni electrode. The cyclic linear micro-polarization experiments, on the other hand, showed that the charge-transfer resistance of the electrochemical reaction at the metal hydride electrode is about twice larger than that of the Ni counterpart above 20% SOC. In comparison, the internal resistance is an order of magnitude smaller than those of the electrochemical charge-transfer reactions. The micro-polarization technique also allowed us to calculate the exchange current densities of the respective electrode electrochemical reactions and the associated specific exchange current densities. These in situ, simple but detailed, characterizations of the thermodynamic and kinetic properties of the Ni-MH system provided valuable information for better understanding of the battery performance.

Users manual for AUTOMESH-2D: A program of automatic mesh generation for two-dimensional scattering analysis by the finite element method

NASA Technical Reports Server (NTRS)

Hua, Chongyu; Volakis, John L.

1990-01-01

AUTOMESH-2D is a computer program specifically designed as a preprocessor for the scattering analysis of two dimensional bodies by the finite element method. This program was developed due to a need for reproducing the effort required to define and check the geometry data, element topology, and material properties. There are six modules in the program: (1) Parameter Specification; (2) Data Input; (3) Node Generation; (4) Element Generation; (5) Mesh Smoothing; and (5) Data File Generation.

February Hydrids (FHY-1032)

NASA Astrophysics Data System (ADS)

Roggemans, Paul; Cambell-Burns, Peter

2018-03-01

CAMS reported an outburst of an unknown minor stream on 14 February 2018, listed in the IAU working list of meteor showers as #1032 FCM (α = 124°, δ = +2°, λʘ = 324°, vg = 16.5 km/s). This analysis shows that many similar orbits can be found in the time span and region in space around the reference orbit. The term 'outburst' is rather misleading as only few orbits were detected during several nights. A search through all public available orbit catalogues resulted in a significant number of similar orbits, but the region proves to be rich in unrelated similar sporadic meteors that fulfill low and medium low D-criteria. This case study on the possible February Hydrids did not result in a convincing evidence for the existence of this minor shower. Both the distribution of the number of similar orbits and the spreading in space indicate the possible presence of a diffuse minor shower without any distinct peak activity. This is a case of a barely detectable minor stream.

MANN: A program to transfer designs for diffractive optical elements to a MANN photolithographic mask generator

NASA Technical Reports Server (NTRS)

Matthys, Donald R.

1994-01-01

There are two basic areas of interest for diffractive optics. In the first, the property of wavefront division is exploited for achieving optical fanout, analogous to the more familiar electrical fanout of electronic circuitry. The basic problem here is that when using a simple uniform diffraction grating the energy input is divided unevenly among the output beams. The other area of interest is the use of diffractive elements to replace or supplement standard refractive elements such as lenses. Again, local grating variations can be used to control the amount of bending imparted to optical rays, and the efficiency of the diffractive element will depend on how closely the element can be matched to the design requirements. In general, production restrictions limit how closely the element approaches the design, and for the common case of photolithographic production, a series of binary masks is required to achieve high efficiency. The actual design process is much more involved than in the case of elements for optical fanout, as the desired phase of the optical wavefront over some reference plane must be specified and the phase alteration to be introduced at each point by the diffraction element must be known. This generally requires the utilization of a standard optical design program. Two approaches are possible. In the first approach, the diffractive element is treated as a special type of lens and the ordinary optical design equations are used. Optical design programs tend to follow a second approach, namely, using the equations of optical interference derived from holographic theory and then allowing the introduction of phase front corrections in the form of polynomial equations. By using either of these two methods, diffractive elements can be used not only to compensate for distortions such as chromatic or spherical aberration, but also to perform the work of a variety of other optical elements such as null correctors, beam shapers, etc. The main focus of the

Research on Finite Element Model Generating Method of General Gear Based on Parametric Modelling

NASA Astrophysics Data System (ADS)

Lei, Yulong; Yan, Bo; Fu, Yao; Chen, Wei; Hou, Liguo

2017-06-01

Aiming at the problems of low efficiency and poor quality of gear meshing in the current mainstream finite element software, through the establishment of universal gear three-dimensional model, and explore the rules of unit and node arrangement. In this paper, a finite element model generation method of universal gear based on parameterization is proposed. Visual Basic program is used to realize the finite element meshing, give the material properties, and set the boundary / load conditions and other pre-processing work. The dynamic meshing analysis of the gears is carried out with the method proposed in this pape, and compared with the calculated values to verify the correctness of the method. The method greatly shortens the workload of gear finite element pre-processing, improves the quality of gear mesh, and provides a new idea for the FEM pre-processing.

Cubic and orthorhombic structures of aluminum hydride Al H3 predicted by a first-principles study

NASA Astrophysics Data System (ADS)

Ke, Xuezhi; Kuwabara, Akihide; Tanaka, Isao

2005-05-01

The most stable structure of aluminum hydride AlH3 is believed to be a hexagonal symmetry. However, using the density functional theory, we have identified two more stable structures for the AlH3 with the cubic and orthorhombic symmetries. Based on the quasiharmonic approximation, the cubic and orthorhombic AlH3 are almost degenerate when the zero-point energies are included. The geometric and electronic structures, the phonon, and the thermodynamic properties for the hexagonal, cubic, and orthorhombic AlH3 have been studied by means of density functional theory and direct ab initio force constant approach. The calculated electronic structures, phonon density of states, and thermodynamic functions [including S(T) and H(T)-H(0) ] for the three hydrides are similar. The results show that these three hydrides have negative enthalpies of formation, but positive free energies of formation. This conclusion is the same as that made by Wolverton for the hexagonal AlH3 [Phys. Rev. B 69, 144109 (2004)]. The thermodynamic properties indicate that the orthorhombic and cubic AlH3 should be more difficult to dissociate than the hexagonal AlH3 .

On-line determination of Sb(III) and total Sb using baker's yeast immobilized on polyurethane foam and hydride generation inductively coupled plasma optical emission spectrometry

NASA Astrophysics Data System (ADS)

Menegário, Amauri A.; Silva, Ariovaldo José; Pozzi, Eloísa; Durrant, Steven F.; Abreu, Cassio H.

2006-09-01

The yeast Saccharomyces cerevisiae was immobilized in cubes of polyurethane foam and the ability of this immobilized material to separate Sb(III) and Sb(V) was investigated. A method based on sequential determination of total Sb (after on-line reduction of Sb(V) to Sb(III) with thiourea) and Sb(III) (after on-line solid-liquid phase extraction) by hydride generation inductively coupled plasma optical emission spectrometry is proposed. A flow system assembled with solenoid valves was used to manage all stages of the process. The effects of pH, sample loading and elution flow rates on solid-liquid phase extraction of Sb(III) were evaluated. Also, the parameters related to on-line pre-reduction (reaction coil and flow rates) were optimized. Detection limits of 0.8 and 0.15 μg L - 1 were obtained for total Sb and Sb(III), respectively. The proposed method was applied to the analysis of river water and effluent samples. The results obtained for the determination of total Sb were in agreement with expected values, including the river water Standard Reference Material 1640 certified by the National Institute of Standards and Technology (NIST). Recoveries of Sb(III) and Sb(V) in spiked samples were between 81 ± 19 and 111 ±15% when 120 s of sample loading were used.

Continuous/Batch Mg/MgH2/H2O-Based Hydrogen Generator

NASA Technical Reports Server (NTRS)

Kindler, Andrew; Huang, Yuhong

2010-01-01

A proposed apparatus for generating hydrogen by means of chemical reactions of magnesium and magnesium hydride with steam would exploit the same basic principles as those discussed in the immediately preceding article, but would be designed to implement a hybrid continuous/batch mode of operation. The design concept would simplify the problem of optimizing thermal management and would help to minimize the size and weight necessary for generating a given amount of hydrogen.

NASTRAN data generation of helicopter fuselages using interactive graphics. [preprocessor system for finite element analysis using IBM computer

NASA Technical Reports Server (NTRS)

Sainsbury-Carter, J. B.; Conaway, J. H.

1973-01-01

The development and implementation of a preprocessor system for the finite element analysis of helicopter fuselages is described. The system utilizes interactive graphics for the generation, display, and editing of NASTRAN data for fuselage models. It is operated from an IBM 2250 cathode ray tube (CRT) console driven by an IBM 370/145 computer. Real time interaction plus automatic data generation reduces the nominal 6 to 10 week time for manual generation and checking of data to a few days. The interactive graphics system consists of a series of satellite programs operated from a central NASTRAN Systems Monitor. Fuselage structural models including the outer shell and internal structure may be rapidly generated. All numbering systems are automatically assigned. Hard copy plots of the model labeled with GRID or elements ID's are also available. General purpose programs for displaying and editing NASTRAN data are included in the system. Utilization of the NASTRAN interactive graphics system has made possible the multiple finite element analysis of complex helicopter fuselage structures within design schedules.

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

NASA Astrophysics Data System (ADS)

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

2016-02-01

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

SSH2S: Hydrogen storage in complex hydrides for an auxiliary power unit based on high temperature proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Baricco, Marcello; Bang, Mads; Fichtner, Maximilian; Hauback, Bjorn; Linder, Marc; Luetto, Carlo; Moretto, Pietro; Sgroi, Mauro

2017-02-01

The main objective of the SSH2S (Fuel Cell Coupled Solid State Hydrogen Storage Tank) project was to develop a solid state hydrogen storage tank based on complex hydrides and to fully integrate it with a High Temperature Proton Exchange Membrane (HT-PEM) fuel cell stack. A mixed lithium amide/magnesium hydride system was used as the main storage material for the tank, due to its high gravimetric storage capacity and relatively low hydrogen desorption temperature. The mixed lithium amide/magnesium hydride system was coupled with a standard intermetallic compound to take advantage of its capability to release hydrogen at ambient temperature and to ensure a fast start-up of the system. The hydrogen storage tank was designed to feed a 1 kW HT-PEM stack for 2 h to be used for an Auxiliary Power Unit (APU). A full thermal integration was possible thanks to the high operation temperature of the fuel cell and to the relative low temperature (170 °C) for hydrogen release from the mixed lithium amide/magnesium hydride system.

A small portable proton exchange membrane fuel cell and hydrogen generator for medical applications.

PubMed

Adlhart, O J; Rohonyi, P; Modroukas, D; Driller, J

1997-01-01

Small, lightweight power sources for total artificial hearts (TAH), left ventricular assist devices (LVAD), and other medical products are under development. The new power source will provide 2 to 3 times the capacity of conventional batteries. The implications of this new power source are profound. For example, for the Heartmate LVAD, 5 to 8 hours of operation are obtained with 3 lb of lead acid batteries (Personal Communication Mr. Craig Sherman, Thermo Cardiosystems, Inc TCI 11/29/96). With the same weight, as much as 14 hours of operation appear achievable with the proton exchange membrane (PEM) fuel cell power source. Energy densities near 135 watt-hour/L are achievable. These values significantly exceed those of most conventional and advanced primary and secondary batteries. The improvement is mission dependent and even applies for the short deployment cited above. The comparison to batteries becomes even more favorable if the mission length is increased. The higher capacity requires only replacement of lightweight hydride cartridges and logistically available water. Therefore, when one spare 50 L hydride cartridge weighing 115 g is added to the reactant supply the energy density of the total system increases to 230 watt-hour/kg. This new power source is comprised of a hydrogen fueled, air-breathing PEM fuel cell and a miniature hydrogen generator (US Patent No 5,514,353). The fuel cell is of novel construction and differs from conventional bipolar PEM fuel cells by the arrangement of cells on a single sheet of ion-exchange membrane. The construction avoids the weight and volume penalty of conventional bipolar stacks. The hydrogen consumed by the fuel cell is generated load-responsively in the miniature hydrogen generator, by reacting calcium hydride with water, forming in the process hydrogen and lime. The generator is cartridge rechargeable and available in capacities providing up to several hundred watt-hours of electric power.

METHOD OF MAKING DELTA ZIRCONIUM HYDRIDE MONOLITHIC MODERATOR PIECES

DOEpatents

Vetrano, J.B.

1962-01-23

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

Aluminum Hydride as a Fuel Supplement to NanoThermites

DTIC Science & Technology

2014-01-01

nanocomposite thermite based on CuO, Bi2O3, and Fe2O3. Pressure cell and burn tube experiments demonstrated enhancements in absolute pressure...pressurization rate, and burning velocity when micron-scale aluminum hydride was used as a minor fuel component in a nanoaluminum–copper-oxide thermite ...alane, AlH3) replaced nanoaluminum incrementally as a fuel in a nanocomposite thermite based on CuO, Bi2O3, and Fe2O3. Pressure cell and burn tube

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chakraborty, Pritam; Sabharwall, Piyush; Spears, Robert Edward

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.

A comparative evaluation of different ionic liquids for arsenic species separation and determination in wine varietals by liquid chromatography - hydride generation atomic fluorescence spectrometry.

PubMed

Castro Grijalba, Alexander; Fiorentini, Emiliano F; Martinez, Luis D; Wuilloud, Rodolfo G

2016-09-02

The application of different ionic liquids (ILs) as modifiers for chromatographic separation and determination of arsenite [As(III)], arsenate [As(V)], dimethylarsonic acid (DMA) and monomethylarsonic acid (MMA) species in wine samples, by reversed-phase high performance liquid chromatography coupled to hydride generation atomic fluorescence spectrometry detection (RP-HPLC-HG-AFS) was studied in this work. Several factors influencing the chromatographic separation of the As species, such as pH of the mobile phase, buffer solution concentration, buffer type, IL concentration and length of alkyl groups in ILs were evaluated. The complete separation of As species was achieved using a C18 column in isocratic mode with a mobile phase composed of 0.5% (v/v) 1-octyl-3-methylimidazolium chloride ([C8mim]Cl) and 5% (v/v) methanol at pH 8.5. A multivariate methodology was used to optimize the variables involved in AFS detection of As species after they were separated by HPLC. The ILs showed remarkable performance for the separation of As species, which was obtained within 18min with a resolution higher than 0.83. The limits of detection for As(III), As(V), MMA and DMA were 0.81, 0.89, 0.62 and 1.00μg As L(-1). The proposed method was applied for As speciation analysis in white and red wine samples originated from different grape varieties. Copyright © 2016 Elsevier B.V. All rights reserved.

Effect of amorphous Mg{sub 50}Ni{sub 50} on hydriding and dehydriding behavior of Mg{sub 2}Ni alloy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guzman, D., E-mail: danny.guzman@uda.cl; Ordonez, S.; Fernandez, J.F.

Composite Mg{sub 2}Ni (25 wt.%) amorphous Mg{sub 50}Ni{sub 50} was prepared by mechanical milling starting with nanocrystalline Mg{sub 2}Ni and amorphous Mg{sub 50}Ni{sub 50} powders, by using a SPEX 8000 D mill. The morphological and microstructural characterization of the powders was performed via scanning electron microscopy and X-ray diffraction. The hydriding characterization of the composite was performed via a solid gas reaction method in a Sievert's-type apparatus at 363 K under an initial hydrogen pressure of 2 MPa. The dehydriding behavior was studied by differential thermogravimetry. On the basis of the results, it is possible to conclude that amorphous Mg{submore » 50}Ni{sub 50} improved the hydriding and dehydriding kinetics of Mg{sub 2}Ni alloy upon cycling. A tentative rationalization of experimental observations is proposed. - Research Highlights: {yields} First study of the hydriding behavior of composite Mg{sub 2}Ni (25 wt.%) amorphous Mg{sub 50}Ni{sub 50}. {yields} Microstructural characterization of composite material using XRD and SEM was obtained. {yields} An improved effect of Mg{sub 50}Ni{sub 50} on the Mg{sub 2}Ni hydriding behavior was verified. {yields} The apparent activation energy for the hydrogen desorption of composite was obtained.« less

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

PubMed

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.

Automated quadrilateral surface discretization method and apparatus usable to generate mesh in a finite element analysis system

DOEpatents

Blacker, Teddy D.

1994-01-01

An automatic quadrilateral surface discretization method and apparatus is provided for automatically discretizing a geometric region without decomposing the region. The automated quadrilateral surface discretization method and apparatus automatically generates a mesh of all quadrilateral elements which is particularly useful in finite element analysis. The generated mesh of all quadrilateral elements is boundary sensitive, orientation insensitive and has few irregular nodes on the boundary. A permanent boundary of the geometric region is input and rows are iteratively layered toward the interior of the geometric region. Also, an exterior permanent boundary and an interior permanent boundary for a geometric region may be input and the rows are iteratively layered inward from the exterior boundary in a first counter clockwise direction while the rows are iteratively layered from the interior permanent boundary toward the exterior of the region in a second clockwise direction. As a result, a high quality mesh for an arbitrary geometry may be generated with a technique that is robust and fast for complex geometric regions and extreme mesh gradations.

Determination of inorganic arsenic in algae using bromine halogenation and on-line nonpolar solid phase extraction followed by hydride generation atomic fluorescence spectrometry.

PubMed

Zhang, Weihong; Qi, Yuehan; Qin, Deyuan; Liu, Jixin; Mao, Xuefei; Chen, Guoying; Wei, Chao; Qian, Yongzhong

2017-08-01

Accurate, stable and fast analysis of toxic inorganic arsenic (iAs) in complicated and arsenosugar-rich algae matrix is always a challenge. Herein, a novel analytical method for iAs in algae was reported, using bromine halogenation and on-line nonpolar solid phase extraction (SPE) followed by hydride generation atomic fluorescence spectrometry (HG-AFS). The separation of iAs from algae was first performed by nonpolar SPE sorbent using Br - for arsenic halogenation. Algae samples were extracted with 1% perchloric acid. Then, 1.5mL extract was reduced by 1% thiourea, and simultaneously reacted (for 30min) with 50μL of 10% KBr for converting iAs to AsBr 3 after adding 3.5mL of 70% HCl to 5mL. A polystyrene (PS) resin cartridge was employed to retain arsenicals, which were hydrolyzed, eluted from the PS resin with H 2 O, and categorized as iAs. The total iAs was quantified by HG-AFS. Under optimum conditions, the spiked recoveries of iAs in real algae samples were in the 82-96% range, and the method achieved a desirable limit of detection of 3μgkg -1 . The inter-day relative standard deviations were 4.5% and 4.1% for spiked 100 and 500μgkg -1 respectively, which proved acceptable for this method. For real algae samples analysis, the highest presence of iAs was found in sargassum fusiforme, followed by kelp, seaweed and laver. Copyright © 2017 Elsevier B.V. All rights reserved.

Development of nickel/metal-hydride batteries for EVs and HEVs

NASA Astrophysics Data System (ADS)

Taniguchi, Akihiro; Fujioka, Noriyuki; Ikoma, Munehisa; Ohta, Akira

This paper is to introduce the nickel/metal-hydride (Ni/MH) batteries for electric vehicles (EVs) and hybrid electric vehicles (HEVs) developed and mass-produced by our company. EV-95 for EVs enables a vehicle to drive approximately 200 km per charge. As the specific power is extremely high, more than 200 W/kg at 80% depth of discharge (DOD), the acceleration performance is equivalent to that of gasoline fuel automobiles. The life characteristic is also superior. This battery gives the satisfactory result of more than 1000 cycles in bench tests and approximately 4-year on-board driving. EV-28 developed for small EVs comprises of a compact and light battery module with high specific power of 300 W/kg at 80% DOD by introducing a new technology for internal cell connection. Meanwhile, our cylindrical battery for the HEV was adopted into the first generation Toyota Prius in 1997 which is the world's first mass-product HEV, and has a high specific power of 600 W/kg. Its life characteristic was found to be equivalent to more than 100,000 km driving. Furthermore, a new prismatic module in which six cells are connected internally was used for the second generation Prius in 2000. The prismatic battery comprises of a compact and light battery pack with a high specific power of 1000 W/kg, which is approximately 1.7 times that of conventional cylindrical batteries, as a consequence of the development of a new internal cell connection and a new current collection structure.

Hydrogen isotope exchange in a metal hydride tube

DOE Office of Scientific and Technical Information (OSTI.GOV)

Robinson, David B.

2014-09-01

This report describes a model of the displacement of one hydrogen isotope within a metal hydride tube by a different isotope in the gas phase that is blown through the tube. The model incorporates only the most basic parameters to make a clear connection to the theory of open-tube gas chromatography, and to provide a simple description of how the behavior of the system scales with controllable parameters such as gas velocity and tube radius. A single tube can be seen as a building block for more complex architectures that provide higher molar flow rates or other advanced design goals.

Modeling of hydride precipitation and re-orientation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tikare, Veena; Weck, Philippe F.; Mitchell, John Anthony

In this report, we present a thermodynamic-­based model of hydride precipitation in Zr-based claddings. The model considers the state of the cladding immediately following drying, after removal from cooling-pools, and presents the evolution of precipitate formation upon cooling as follows: The pilgering process used to form Zr-based cladding imparts strong crystallographic and grain shape texture, with the basal plane of the hexagonal α-Zr grains being strongly aligned in the rolling-­direction and the grains are elongated with grain size being approximately twice as long parallel to the rolling direction, which is also the long axis of the tubular cladding, as itmore » is in the orthogonal directions.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smetana, Volodymyr; Mudring, Anja-Verena

2016-10-24

With Cs9Pt4H a new representative of ionic compounds featuring metal anions can be added to this rare-membered family. Cs 9Pt 4H exhibits a complex crystal structure containing Cs + cations, Pt 2- and H - anions. Being a red, transparent compound its band gap is in the visible range of the electromagnetic spectrum and the ionic type of bonding is confirmed by quantum chemical calculations. This cesium platinide hydride can formally be considered as a double salt of the “alloy” cesium–platinum, or better cesium platinide, Cs2Pt, and the salt cesium hydride CsH according to Cs 9Pt 4H≡4 Cs 2Pt∙CsH.

Processing and properties of Ti-6Al-4V hollow sphere foams from hydride powder

NASA Astrophysics Data System (ADS)

Hardwicke, Canan Uslu

Honeycomb structures currently used in aerospace systems are expensive to manufacture, limited to sheet form, and present joining problems and mechanical anisotropy that promotes shear failure at low stresses. Metallic foams produced by point contact bonding of monosized hollow spheres offer an alternative if they can be processed into strong, light-weight, and reasonably priced structural materials. In this work, technology has been established for fabricating good quality, Ti-6Al-4V hollow sphere foams using the coaxial nozzle powder slurry technique. It was shown that hydride form of Ti-ELI can be used as the starting precursor powder and processed into fine particles of 1-10 mum size range without increasing the impurity levels. Hydride dispersion in acetone was provided by the addition of polyester/polyamine copolymers through electrosteric stabilization. Addition of PMMA to the pseudoplastically dispersed organic slurries helped bind hydride powder spherical shells. Furthermore, monosized Ti-6Al-4V hollow spheres were sintered to 98% dense cell walls in Ar and point-contact bonded into closed-cell foams through solid-state diffusion. These findings suggest that near-net shape Ti-6Al-4V structures may be produced with isotropic properties, strength, toughness, and densities as low as 10% of the bulk. Findings concerning the optimum processing parameters and implications for future research are discussed.

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

DOE PAGES

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

2016-01-01

This paper presents a design analysis for the development of highly efficient heat exchangers within stationary metal hydride heat pumps. The design constraints and selected performance criteria are applied to three representative heat exchangers. The proposed thermal model can be applied to select the most efficient heat exchanger design and provides outcomes generally valid in a pre-design stage. Heat transfer effectiveness is the principal performance parameter guiding the selection analysis, the results of which appear to be mildly (up to 13%) affected by the specific Nusselt correlation used. The thermo-physical properties of the heat transfer medium and geometrical parameters aremore » 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 heat exchanger are identified by finding the conditions over which the heat removal from the solid bed enables a complete and continuous hydriding reaction. The most efficient solution is a design example that achieves the target effectiveness of 95%.« less

New Possibilities for Understanding Complex Metal Hydrides via Synchrotron X-ray Studies

NASA Astrophysics Data System (ADS)

Dobbins, Tabbetha

2008-03-01

Ultrasmall-angle x-ray scattering (USAXS) and X-ray absorption spectroscopy (XAS) are used for the study of chemical and morphological changes in metal hydride powder (e.g. NaAlH4) both before and after transition metal salt catalytic dopant additions by high energy ball milling. The variation in surface fractal dimension and particle size with milling time and dopant content were tracked. These studies show that dopant content level (e.g. 2 mol % and 4 mol %) and dopant type (i.e. TiCl2, TiCl3, VCl3, and ZrCl4) markedly affects NaAlH4 powder particle surface area (determined using USAXS surface fractal dimension). As well, the chemical reaction between the catalyst and hydride powder was further elucidated using XAS. Ti-metal reacts with the Al desorption product (from NaAlH4) to form TiAlx product phases. These studies were able to link powder particle surface area to catalytic doping and were able to link dopant chemical state with dehydrogenation reactant and product phases.

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

NASA Astrophysics Data System (ADS)

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

2016-10-01

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

Solar fuels: visible-light-driven generation of dihydrogen at p-type silicon electrocatalysed by molybdenum hydrides.

PubMed

Webster, Lee R; Ibrahim, Saad K; Wright, Joseph A; Pickett, Christopher J

2012-09-10

We show that a robust molybdenum hydride system can sustain photoelectrocatalysis of a hydrogen evolution reaction at boron-doped, hydrogen-terminated, p-type silicon. The photovoltage for the system is about 600-650 mV and the current densities, which can be sustained at the photocathode in non-catalytic and catalytic regimes, are similar to those at a photoinert vitreous carbon electrode. The kinetics of electrocatalysed hydrogen evolution at the photocathode are also very similar to those measured at vitreous carbon-evidently visible light does not significantly perturb the catalytic mechanism. Importantly, we show that the doped (1-10 Ω cm) p-type Si can function perfectly well in the dark as an ohmic conductor and this has allowed direct comparison of the cyclic voltammetric behaviour of the response of the system under dark and illuminated conditions at the same electrode. The p-type Si we have employed optimally harvests light energy in the 600-700 nm region and with 37 mW cm(-2) illumination in this range; the light to electrochemical energy conversion is estimated to be 2.8 %. The current yield of hydrogen under broad tungsten halide lamp illumination at 90 mW cm(-2) is (91±5) % with a corresponding chemical yield of (98±5) %. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydride reorientation and its impact on ambient temperature mechanical properties of high burn-up irradiated and unirradiated recrystallized Zircaloy-2 nuclear fuel cladding with an inner liner

NASA Astrophysics Data System (ADS)

Auzoux, Q.; Bouffioux, P.; Machiels, A.; Yagnik, S.; Bourdiliau, B.; Mallet, C.; Mozzani, N.; Colas, K.

2017-10-01

Precipitation of radial hydrides in zirconium-based alloy cladding concomitant with the cooling of spent nuclear fuel during dry storage can potentially compromise cladding integrity during its subsequent handling and transportation. This paper investigates hydride reorientation and its impact on ductility in unirradiated and irradiated recrystallized Zircaloy-2 cladding with an inner liner (cladding for boiling water reactors) subjected to hydride reorientation treatments. Cooling from 400 °C, hydride reorientation occurs in recrystallized Zircaloy-2 with liner at a lower effective stress in irradiated samples (below 40 MPa) than in unirradiated specimens (between 40 and 80 MPa). Despite significant hydride reorientation, unirradiated recrystallized Zircaloy-2 with liner cladding containing ∼200 wppm hydrogen shows a high diametral strain at fracture (>15%) during burst tests at ambient temperature. This ductile behavior is due to (1) the lower yield stress of the recrystallized cladding materials in comparison to hydride fracture strength (corrected by the compression stress arising from the precipitation) and (2) the hydride or hydrogen-depleted zone as a result of segregation of hydrogen into the liner layer. In irradiated Zircaloy-2 with liner cladding containing ∼340 wppm hydrogen, the conservation of some ductility during ring tensile tests at ambient temperature after reorientation treatment at 400 °C with cooling rates of ∼60 °C/h is also attributed to the existence of a hydride-depleted zone. Treatments at lower cooling rates (∼6 °C/h and 0.6 °C/h) promote greater levels of hydrogen segregation into the liner and allow for increased irradiation defect annealing, both of which result in a significant increase in ductility. Based on this investigation, given the very low cooling rates typical of dry storage systems, it can be concluded that the thermal transients associated with dry storage should not degrade, and more likely should actually

Design and Characterization of Phosphine Iron Hydrides: Toward Hydrogen-Producing Catalysts.

PubMed

Weber, Katharina; Weyhermüller, Thomas; Bill, Eckhard; Erdem, Özlen F; Lubitz, Wolfgang

2015-07-20

Diamagnetic iron chloro compounds [(P(Ph)2N(Ph)2)FeCp*Cl] [1Cl] and [(P(Cy)2N(Ph)2)FeCp*Cl] [2Cl] and the corresponding hydrido complexes [(P(Ph)2N(Ph)2)FeCp*H] [1H] and [(P(Cy)2N(Ph)2)FeCp*H] [2H] have been synthesized and characterized by NMR spectroscopy, electrochemical studies, electronic absorption, and (57)Fe Mössbauer spectroscopy (P(Ph)2N(Ph)2 = 1,3,5,7-tetraphenyl-1,5-diphospha-3,7-diazacyclooctane, P(Cy)2N(Ph)2 = 1,5-dicyclohexyl-3,7-diphenyl-1,5-diphospha-3,7-diazacyclooctane, Cp* = pentamethylcyclopentadienyl). Molecular structures of [2Cl], [1H], and [2H], derived from single-crystal X-ray diffraction, revealed that these compounds have a typical piano-stool geometry. The results show that the electronic properties of the hydrido complexes are strongly influenced by the substituents at the phosphorus donor atoms of the P(R)2N(Ph)2 ligand, whereas those of the chloro complexes are less affected. These results illustrate that the hydride is a strong-field ligand, as compared to chloride, and thus leads to a significant degree of covalent character of the iron hydride bonds. This is important in the context of possible catalytic intermediates of iron hydrido species, as proposed for the catalytic cycle of [FeFe] hydrogenases and other synthetic catalysts. Both hydrido compounds [1H] and [2H] show enhanced catalytic currents in cyclic voltammetry upon addition of the strong acid trifluoromethanesulfonimide [NHTf2] (pKa(MeCN) = 1.0). In contrast to the related complex [(P(tBu)N(Bn))2FeCp(C6F5)H], which was reported by Liu et al. (Nat. Chem. 2013, 5, 228-233) to be an electrocatalyst for hydrogen splitting, the here presented hydride complexes [1H] and [2H] show the tendency for electrocatalytic hydrogen production. Hence, the catalytic direction of this class of monoiron compounds can be reversed by specific ligand modifications.

Hydrogen Storage Engineering Center of Excellence Metal Hydride Final Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Motyka, T.

2014-05-31

The Hydrogen Storage Engineering Center of Excellence (HSECoE) was established in 2009 by the U.S. Department of Energy (DOE) to advance the development of materials-based hydrogen storage systems for hydrogen-fueled light-duty vehicles. The overall objective of the HSECoE is to develop complete, integrated system concepts that utilize reversible metal hydrides, adsorbents, and chemical hydrogen storage materials through the use of advanced engineering concepts and designs that can simultaneously meet or exceed all the DOE targets. This report describes the activities and accomplishments during Phase 1 of the reversible metal hydride portion of the HSECoE, which lasted 30 months from Februarymore » 2009 to August 2011. A complete list of all the HSECoE partners can be found later in this report but for the reversible metal hydride portion of the HSECoE work the major contributing organizations to this effort were the United Technology Research Center (UTRC), General Motors (GM), Pacific Northwest National Laboratory (PNNL), the National Renewable Energy Laboratory (NREL) and the Savannah River National Laboratory (SRNL). Specific individuals from these and other institutions that supported this effort and the writing of this report are included in the list of contributors and in the acknowledgement sections of this report. The efforts of the HSECoE are organized into three phases each approximately 2 years in duration. In Phase I, comprehensive system engineering analyses and assessments were made of the three classes of storage media that included development of system level transport and thermal models of alternative conceptual storage configurations to permit detailed comparisons against the DOE performance targets for light-duty vehicles. Phase 1 tasks also included identification and technical justifications for candidate storage media and configurations that should be capable of reaching or exceeding the DOE targets. Phase 2 involved bench-level testing and

Nonempirical Calculation of Superconducting Transition Temperatures in Light-Element Superconductors.

PubMed

Arita, Ryotaro; Koretsune, Takashi; Sakai, Shiro; Akashi, Ryosuke; Nomura, Yusuke; Sano, Wataru

2017-07-01

Recent progress in the fully nonempirical calculation of the superconducting transition temperature (T c ) is reviewed. Especially, this study focuses on three representative light-element high-T c superconductors, i.e., elemental Li, sulfur hydrides, and alkali-doped fullerides. Here, it is discussed how crucial it is to develop the beyond Migdal-Eliashberg (ME) methods. For Li, a scheme of superconducting density functional theory for the plasmon mechanism is formulated and it is found that T c is dramatically enhanced by considering the frequency dependence of the screened Coulomb interaction. For sulfur hydrides, it is essential to go beyond not only the static approximation for the screened Coulomb interaction, but also the constant density-of-states approximation for electrons, the harmonic approximation for phonons, and the Migdal approximation for the electron-phonon vertex, all of which have been employed in the standard ME calculation. It is also shown that the feedback effect in the self-consistent calculation of the self-energy and the zero point motion considerably affect the calculation of T c . For alkali-doped fullerides, the interplay between electron-phonon coupling and electron correlations becomes more nontrivial. It has been demonstrated that the combination of density functional theory and dynamical mean field theory with the ab initio downfolding scheme for electron-phonon coupled systems works successfully. This study not only reproduces the experimental phase diagram but also obtains a unified view of the high-T c superconductivity and the Mott-Hubbard transition in the fullerides. The results for these high-T c superconductors will provide a firm ground for future materials design of new superconductors. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The calculated rovibronic spectrum of scandium hydride, ScH

NASA Astrophysics Data System (ADS)

Lodi, Lorenzo; Yurchenko, Sergei N.; Tennyson, Jonathan

2015-07-01

The electronic structure of six low-lying electronic states of scandium hydride, X 1Σ+, a 3Δ, b 3Π, A 1Δ, c 3Σ+ and B 1Π, 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 rovibronic transitions for 45ScH.

Production of Hydrogen by Electrocatalysis: Making the H-H Bond by Combining Protons and Hydrides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bullock, R. Morris; Appel, Aaron M.; Helm, Monte L.

2014-03-25

Generation of hydrogen by reduction of two protons by two electrons can be catalysed by molecular electrocatalysts. Determination of the thermodynamic driving force for elimination of H2 from molecular complexes is important for the rational design of molecular electrocatalysts, and allows the design of metal complexes of abundant, inexpensive metals rather than precious metals (“Cheap Metals for Noble Tasks”). The rate of H2 evolution can be dramatically accelerated by incorporating pendant amines into diphosphine ligands. These pendant amines in the second coordination sphere function as protons relays, accelerating intramolecular and intermolecular proton transfer reactions. The thermodynamics of hydride transfer frommore » metal hydrides and the acidity of protonated pendant amines (pKa of N-H) contribute to the thermodynamics of elimination of H2; both of the hydricity and acidity can be systematically varied by changing the substituents on the ligands. A series of Ni(II) electrocatalysts with pendant amines have been developed. In addition to the thermochemical considerations, the catalytic rate is strongly influenced by the ability to deliver protons to the correct location of the pendant amine. Protonation of the amine endo to the metal leads to the N-H being positioned appropriately to favor rapid heterocoupling with the M-H. Designing ligands that include proton relays that are properly positioned and thermodynamically tuned is a key principle for molecular electrocatalysts for H2 production as well as for other multi-proton, multi-electron reactions important for energy conversions. The research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for DOE.« less

Formation of Gas-Phase Formate in Thermal Reactions of Carbon Dioxide with Diatomic Iron Hydride Anions.

PubMed

Jiang, Li-Xue; Zhao, Chongyang; Li, Xiao-Na; Chen, Hui; He, Sheng-Gui

2017-04-03

The hydrogenation of carbon dioxide involves the activation of the thermodynamically very stable molecule CO 2 and formation of a C-H bond. Herein, we report that HCO 2 - and CO can be formed in the thermal reaction of CO 2 with a diatomic metal hydride species, FeH - . The FeH - anions were produced by laser ablation, and the reaction with CO 2 was analyzed by mass spectrometry and quantum-chemical calculations. Gas-phase HCO 2 - was observed directly as a product, and its formation was predicted to proceed by facile hydride transfer. The mechanism of CO 2 hydrogenation in this gas-phase study parallels similar behavior of a condensed-phase iron catalyst. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stream-sediment samples reanalyzed for major, rare earth, and trace elements from ten 1:250,000-scale quadrangles, south-central Alaska, 2007-08

USGS Publications Warehouse

Bailey, Elizabeth A.; Shew, Nora B.; Labay, Keith A.; Schmidt, Jeanine M.; O'Leary, Richard M.; Detra, David E.

2010-01-01

During the 1960s through the 1980s, the U.S. Geological Survey (USGS) conducted reconnaissance geochemical surveys of the drainage basins throughout most of the Anchorage, Bering Glacier, Big Delta, Gulkana, Healy, McCarthy, Mount Hayes, Nabesna, Talkeetna Mountains, and Valdez 1:250,000-scale quadrangles in Alaska as part of the Alaska Mineral Resource Assessment Program (AMRAP). These geochemical surveys provide data necessary to assess the potential for undiscovered mineral resources on public and other lands, and provide data that may be used to determine regional-scale element baselines. This report provides new data for 366 of the previously collected stream-sediment samples. These samples were selected for reanalysis because recently developed analytical methods can detect additional elements of interest and have lower detection limits than the methods used when these samples were originally analyzed. These samples were all analyzed for arsenic by hydride generation atomic absorption spectrometry (HGAAS), for gold, palladium, and platinum by inductively coupled plasma-mass spectrometry after lead button fire assay separation (FA/ICP-MS), and for a suite of 55 major, rare earth, and trace elements by inductively coupled plasma-atomic emission spectrometry and inductively coupled plasma-mass spectrometry (ICP-AES-MS) after sodium peroxide sinter at 450 degrees Celsius.

Process for production of a metal hydride

DOEpatents

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

2014-08-12

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

Preparation of A356 Foam Aluminum by Means of Titanium Hydride

NASA Astrophysics Data System (ADS)

Sarajan, Zohair

2017-09-01

The effect of heating temperature and stirring time during preparation of foam aluminum alloy A356 on its relative porosity is studied. The optimum amount of the foam-forming agent, i.e., titanium hydride TiH2, facilitating uniform distribution of pores throughout the whole cross section of a hardened casting is determined. Optimum conditions are established for foam formation in a melt during stirring using a mixer are described.

System for operating solid oxide fuel cell generator on diesel fuel

NASA Technical Reports Server (NTRS)

Singh, Prabhu (Inventor); George, Raymond A. (Inventor)

1997-01-01

A system is provided for operating a solid oxide fuel cell generator on diesel fuel. The system includes a hydrodesulfurizer which reduces the sulfur content of commercial and military grade diesel fuel to an acceptable level. Hydrogen which has been previously separated from the process stream is mixed with diesel fuel at low pressure. The diesel/hydrogen mixture is then pressurized and introduced into the hydrodesulfurizer. The hydrodesulfurizer comprises a metal oxide such as ZnO which reacts with hydrogen sulfide in the presence of a metal catalyst to form a metal sulfide and water. After desulfurization, the diesel fuel is reformed and delivered to a hydrogen separator which removes most of the hydrogen from the reformed fuel prior to introduction into a solid oxide fuel cell generator. The separated hydrogen is then selectively delivered to the diesel/hydrogen mixer or to a hydrogen storage unit. The hydrogen storage unit preferably comprises a metal hydride which stores hydrogen in solid form at low pressure. Hydrogen may be discharged from the metal hydride to the diesel/hydrogen mixture at low pressure upon demand, particularly during start-up and shut-down of the system.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hickey, Anne K.; Muñoz, Salvador B.; Lutz, Sean A.

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

A Bimetallic Nickel-Gallium Complex Catalyzes CO2 Hydrogenation via the Intermediacy of an Anionic d10 Nickel Hydride.

PubMed

Cammarota, Ryan C; Vollmer, Matthew V; Xie, Jing; Ye, Jingyun; Linehan, John C; Burgess, Samantha A; Appel, Aaron M; Gagliardi, Laura; Lu, Connie C

2017-10-11

Large-scale CO 2 hydrogenation could offer a renewable stream of industrially important C 1 chemicals while reducing CO 2 emissions. Critical to this opportunity is the requirement for inexpensive catalysts based on earth-abundant metals instead of precious metals. We report a nickel-gallium complex featuring a Ni(0)→Ga(III) bond that shows remarkable catalytic activity for hydrogenating CO 2 to formate at ambient temperature (3150 turnovers, turnover frequency = 9700 h -1 ), compared with prior homogeneous Ni-centered catalysts. The Lewis acidic Ga(III) ion plays a pivotal role in stabilizing catalytic intermediates, including a rare anionic d 10 Ni hydride. Structural and in situ characterization of this reactive intermediate support a terminal Ni-H moiety, for which the thermodynamic hydride donor strength rivals those of precious metal hydrides. Collectively, our experimental and computational results demonstrate that modulating a transition metal center via a direct interaction with a Lewis acidic support can be a powerful strategy for promoting new reactivity paradigms in base-metal catalysis.

A universal algorithm for an improved finite element mesh generation Mesh quality assessment in comparison to former automated mesh-generators and an analytic model.

PubMed

Kaminsky, Jan; Rodt, Thomas; Gharabaghi, Alireza; Forster, Jan; Brand, Gerd; Samii, Madjid

2005-06-01

The FE-modeling of complex anatomical structures is not solved satisfyingly so far. Voxel-based as opposed to contour-based algorithms allow an automated mesh generation based on the image data. Nonetheless their geometric precision is limited. We developed an automated mesh-generator that combines the advantages of voxel-based generation with improved representation of the geometry by displacement of nodes on the object-surface. Models of an artificial 3D-pipe-section and a skullbase were generated with different mesh-densities using the newly developed geometric, unsmoothed and smoothed voxel generators. Compared to the analytic calculation of the 3D-pipe-section model the normalized RMS error of the surface stress was 0.173-0.647 for the unsmoothed voxel models, 0.111-0.616 for the smoothed voxel models with small volume error and 0.126-0.273 for the geometric models. The highest element-energy error as a criterion for the mesh quality was 2.61x10(-2) N mm, 2.46x10(-2) N mm and 1.81x10(-2) N mm for unsmoothed, smoothed and geometric voxel models, respectively. The geometric model of the 3D-skullbase resulted in the lowest element-energy error and volume error. This algorithm also allowed the best representation of anatomical details. The presented geometric mesh-generator is universally applicable and allows an automated and accurate modeling by combining the advantages of the voxel-technique and of improved surface-modeling.

Water in star-forming regions with Herschel (WISH). VI. Constraints on UV and X-ray irradiation from a survey of hydrides in low- to high-mass young stellar objects

NASA Astrophysics Data System (ADS)

Benz, A. O.; Bruderer, S.; van Dishoeck, E. F.; Melchior, M.; Wampfler, S. F.; van der Tak, F.; Goicoechea, J. R.; Indriolo, N.; Kristensen, L. E.; Lis, D. C.; Mottram, J. C.; Bergin, E. A.; Caselli, P.; Herpin, F.; Hogerheijde, M. R.; Johnstone, D.; Liseau, R.; Nisini, B.; Tafalla, M.; Visser, R.; Wyrowski, F.

2016-05-01

Context. Hydrides are simple compounds containing one or a few hydrogen atoms bonded to a heavier atom. They 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+), which affect the chemistry of molecules such as water, provide complementary information on irradiation by far-UV (FUV) or X-rays and gas temperature. Aims: We explore hydrides of the most abundant heavier elements in an observational survey covering young stellar objects (YSOs) with different mass and evolutionary state. The focus is on hydrides associated with the dense protostellar envelope and outflows, contrary to previous work that focused on hydrides in diffuse foreground clouds. Methods: Twelve YSOs were observed with HIFI on Herschel in six spectral settings providing fully velocity-resolved line profiles as part of the Water in star-forming regions with Herschel (WISH) program. The YSOs include objects of low (Class 0 and I), intermediate, and high mass, with luminosities ranging from 4 L⊙ to 2 × 105 L⊙. Results: The targeted lines of CH+, OH+, H2O+, C+, and CH are detected mostly in blue-shifted absorption. H3O+ and SH+ are detected in emission and only toward some high-mass objects. The observed line parameters and correlations suggest two different origins related to gas entrained by the outflows and to the circumstellar envelope. The derived column densities correlate with bolometric luminosity and envelope mass for all molecules, best for CH, CH+, and HCO+. The column density ratios of CH+/OH+ are estimated from chemical slab models, assuming that the H2 density is given by the specific density model of each object at the beam radius. For the low-mass YSOs the observed ratio can be reproduced for an FUV flux of 2-400 times the interstellar radiation field (ISRF) at the location of the molecules. In two high

Identification of a new pseudo-binary hydroxide during calendar corrosion of (La, Mg)2Ni7-type hydrogen storage alloys for Nickel-Metal Hydride batteries

NASA Astrophysics Data System (ADS)

Monnier, J.; Chen, H.; Joiret, S.; Bourgon, J.; Latroche, M.

2014-11-01

To improve the performances of Nickel-Metal Hydride batteries, an important step is the understanding of the corrosion processes that take place in the electrode material. In particular, the present study focuses for the first time on the model (La, Mg)2Ni7 system. The calendar corrosion in 8.7 M KOH medium was investigated from 6 h to 16 weeks immersion. By a unique combination of structural and elemental characterisations, the corrosion products are evidenced in those systems. In particular, we demonstrate that Ni and Mg combine in a pseudo-binary hydroxide Mg1-xNix(OH)2 whereas La corrodes into nanoporous La(OH)3 needles with inner hollow nanochannels.

Synthesis and Structural characterization of β-ketoiminate-stabilized gallium hydrides for chemical vapor deposition applications.

PubMed

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

2014-08-11

Bis-β-ketoimine ligands of the form [(CH2 )n {N(H)C(Me)CHC(Me)O}2 ] (L(n) H2 , n=2, 3 and 4) were employed in the formation of a range of gallium complexes [Ga(L(n) )X] (X=Cl, Me, H), which were characterised by NMR spectroscopy, mass spectrometry and single-crystal X-ray diffraction analysis. The β-ketoimine ligands have also been used for the stabilisation of rare gallium hydride species [Ga(L(n) )H] (n=2 (7); n=3 (8)), which have been structurally characterised for the first time, confirming the formation of five-coordinate, monomeric species. The stability of these hydrides has been probed through thermal analysis, revealing stability at temperatures in excess of 200 °C. The efficacy of all the gallium β-ketoiminate complexes as molecular precursors for the deposition of gallium oxide thin films by chemical vapour deposition (CVD) has been investigated through thermogravimetric analysis and deposition studies, with the best results being found for a bimetallic gallium methyl complex [L(3) {GaMe2 }2 ] (5) and the hydride [Ga(L(3) )H] (8). The resulting films (F5 and F8, respectively) were amorphous as-deposited and thus were characterised primarily by XPS, EDXA and SEM techniques, which showed the formation of stoichiometric (F5) and oxygen-deficient (F8) Ga2 O3 thin films. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study of the mechanical behavior of the hydride blister/rim structure in Zircaloy-4 using in-situ synchrotron X-ray diffraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Jun-li; Han, Xiaochun; Heuser, Brent J.

2016-04-01

High-energy synchrotron X-ray diffraction was utilized to study the mechanical response of the f.c.c delta hydride phase, the intermetallic precipitation with hexagonal C14 lave phase and the alpha-Zr phase in the Zircaloy-4 materials with a hydride rim/blister structure near one surface of the material during in-situ uniaxial tension experiment at 200 degrees C. The f.c.c delta was the only hydride phase observed in the rim/blister structure. The conventional Rietveld refinement was applied to measure the macro-strain equivalent response of the three phases. Two regions were delineated in the applied load versus lattice strain measurement: a linear elastic strain region andmore » region that exhibited load partitioning. Load partitioning was quantified by von Mises analysis. The three phases were observed to have similar elastic modulus at 200 degrees C.« less

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

NASA Astrophysics Data System (ADS)

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

2017-05-01

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

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

DOE PAGES

Sung, Z. -H.; Wang, M.; Polyanskii, A. A.; ...

2017-05-19

This study shows that low angle grain boundaries (LAGBs) can be created by small 5% strains in high purity (RRR ≥ 200) SRF-grade single crystalline niobium (Nb) and that these boundaries act as hydrogen traps as indicated by the distribution of niobium hydrides (Nb 1-xH x). Nb 1-xH x is detrimental to superconducting radio frequency (SRF) Nb cavities due to its normal conducting properties at cavity operating temperatures. By designing a single crystal tensile sample extracted from a large grain (>5 cm) Nb ingot slice for preferred slip on one slip plane, LAGBs and dense dislocation boundaries developed. With chemicalmore » surface treatments following standard SRF cavity fabrication practice, Nb1-xHx phases were densely precipitated at the LAGBs upon cryogenic cooling (8-10 K/min). Micro-crystallographic analysis confirmed heterogeneous hydride precipitation, which included significant hydrogen atom accumulation in LAGBs. Magneto-optical imaging (MOI) analysis showed that these sites can then act as sites for both premature flux penetration and eventually flux trapping. However, this hydrogen related degradation at LAGBs did not completely disappear even after a 800 °C/2hrs anneal typically used for hydrogen removal in SRF Nb cavities. These findings suggest that hydride precipitation at a LAGB is facilitated by a non-equilibrium concentration of vacancy-hydrogen (H) complexes aided by mechanical deformation and the hydride phase interferes with the recovery process under 800°C annealing.« less

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

NASA Astrophysics Data System (ADS)

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.

An experimental survey of additives for improving dehydrogenation properties of magnesium hydride