Stabilization of scandium rich spinel ferrite CoFe{sub 2−x}Sc{sub x}O{sub 4} (x≤1) in thin films

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

Lefevre, Christophe, E-mail: christophe.lefevre@ipcms.unistra.fr; Roulland, François; Thomasson, Alexandre

2015-12-15

Scandium rich cobalt ferrites Co{sub y}Fe{sub 3−x−y}Sc{sub x}O{sub 4} with y~1 never obtained in bulk could be stabilized in pulsed laser deposited thin films. Scandium contents of up to x=1 are reached. The cell parameter increases versus x as awaited when considering the size of scandium. It is equal to 0.8620 nm for x=1, significantly higher than that of CoFe{sub 2}O{sub 4} (0.8396 nm). The lattice mismatch between the MgO (100) substrate and the scandium-containing spinel leads to an increased roughness. Cobalt is displaced from the octahedral site by Sc and mainly occupies the tetrahedral sites for high x values.more » - Graphical abstract: Magnification of the XRD patterns recorded on thin films of CoFe{sub 2-x}Sc{sub x}O{sub 4} for x=0, 0.45, 1 and 1.2, the arrows denote the (004) and (008) diffraction lines of the spinel phase.« less

Thermomechanical treatment of welded joints of aluminum-lithium alloys modified by scandium

NASA Astrophysics Data System (ADS)

Malikov, A. G.

2017-12-01

At present, the aeronautical equipment manufacture involves up-to-date high-strength aluminum alloys of decreased density resulting from the lithium admixture. Various technologies of fusible welding of these alloys are being developed. The paper presents experimental investigations of the optimization of the laser welding of aluminum alloys with the scandium-modified welded joint after thermomechanical treatment. The effect of scandium on the micro- and macrostructure is studied along with strength characteristics of the welded joint. It is found that thermomechanical treatment allows us to obtain the strength of the welded joint 0.89 for the Al-Mg-Li system and 0.99 for the Al-Cu-Li system with the welded joint modified by scandium in comparison with the base alloy after treatment.

Solid state lasers based on chromium- and neodymium-activated scandium garnets operating in the Q-switched mode

NASA Astrophysics Data System (ADS)

Denisov, A. L.; Zharikov, E. V.; Zavartsev, Iu. D.; Zagumennyi, A. I.; Lutts, G. B.

1991-02-01

The development of passively Q-switched and self-Q-switched lasers based on chromium-containing scandium garnets with phototropic centers is reported. The lasers operate over a wide frequency repetition rate with a mean output up to 100 W. The characteristics of phototropic absorption in the 1-micron region are examined, and the possibility of lasing at the weak transition of the Nd(3+) ion in chromium-containing scandium garnets with phototropic centers is discussed.

Gadolinium Scandium Gallium Garnet (GSGG) as a Solid-State Laser Host

DTIC Science & Technology

1987-07-01

o*SATI CODSi1.SBEC EM (otne nrvrs fnceayad dniy nb)k ubr ~~~~~~~~ Gadolinium Scandium Gallium Garnet (GSGG)asaSldtteLerHt 17. ABSTRACT 6.SUJCTTEM...certain other garnet materials for replacement. It also addresses the solid-state laser host material Gadolinium Scandium Gal- lium Garnet (GSGG) and its...by neodymium-doped yttrium aluminum garnet (Nd:YAG) or other mate- rials for most applications. In the years after the invention of the ruby laser, in

Influence of scandium on the microstructure and strength properties of the welded joint at the laser welding of aluminum-lithium alloys

NASA Astrophysics Data System (ADS)

Malikov, A. G.; Golyshev, A. A.; Ivanova, M. Yu.

2017-10-01

Today, aeronautical equipment manufacture involves up-to-date high-strength aluminum alloys of decreased density resulting from lithium admixture. Various technologies of fusible welding of these alloys are being developed. Serious demands are imposed to the welded joints of aluminum alloys in respect to their strength characteristics. The paper presents experimental investigations of the optimization of the laser welding of aluminum alloys with the scandium-modified welded joint. The effect of scandium on the micro-and macro-structure has been studied as well as the strength characteristics of the welded joint. It has been found that scandium under in the laser welding process increases the welded joint elasticity for the system Al-Mg-Li, aluminum alloy 1420 by 20 %, and almost doubles the same for the system Al-Cu-Li, aluminum alloy 1441.

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 Å could be obtained with a bulk film oxygen level of ∼0.54 oxygen as determined by microprobe analysis when an evaporation rate of ∼0.313 mg/cm{sup 2} min was used in an atmosphere of D{sub 2} or T{sub 2} gas at a system deposition pressure of 1 × 10{sup −3 }Torr (1.33 × 10{sup −1 }Pa) in an evaporation time of ∼2 min. Platelet type (i.e., a film microstructure showing an overlay of flat plates with large grain sizes) film structures were observed for most films with some film mechanical properties determined (i.e., grain size and Vickers μ-hardness), and reduced stress levels were seen with initial normalized differential (tensile) stress levels being (1.0–4.0) × 10{sup 8 }dyne/cm{sup 2} for tritium loaded samples and (1.5 ± 0.5) × 10{sup 9 }dyne/cm{sup 2} for deuterium loaded samples. Also, stress aging characteristics were determined for some hydride films prepared in a radioactive tritium gas atmosphere. Tritium loading, however, had the undesirable characteristic of having to dispose of the internal processing system fixtures, which can be minimized, but the reactive evaporation technique produced desirable thin films.« less

Selective recovery of vanadium and scandium by ion exchange with D201 and solvent extraction using P507 from hydrochloric acid leaching solution of red mud.

PubMed

Zhu, Xiaobo; Li, Wang; Tang, Sen; Zeng, Majian; Bai, Pengyuan; Chen, Lunjian

2017-05-01

D201 resin and P507 extractant diluted with sulfonated kerosene were used to respectively separate vanadium and scandium, and impurity ions from hydrochloric acid leaching solution of red mud. More than 99% of vanadium was selectively adsorbed from the hydrochloric acid leaching solution under the conditions of pH value of 1.8, volume ratio of leaching solution to resin of 10, and flow rate of 3.33 mL/min. Maximum extraction and separation of scandium was observed from the acid leaching solution at an aqueous pH value of 0.2. More than 99% of scandium can be selectively extracted using 15% P507, 5% TBP at the aqueous solution/organic phase (A/O) ratio of 10:1 for 6 min. The loaded organic phase was washed with 0.3 mol/L sulfuric acid, wherein most impurities were removed. After the process of desorption or stripping, precipitation, and roasting, high-purity V 2 O 5 and Sc 2 O 3 were obtained. Finally, a conceptual flow sheet was established to separate and recover vanadium and scandium from red mud hydrochloric acid leaching solution. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effect of scandium on the phase composition and mechanical properties of ABM alloys

NASA Astrophysics Data System (ADS)

Molchanova, L. V.

2010-09-01

The effect of scandium on the composition and mechanical properties of ABM-1 alloys (Al-30% Be-5% Mg) is studied. The scandium content is varied from 0.1 to 0.5 wt %. It is established that, in the studied part of the Al-Be-Mg-Sc system, an aluminum solid solution (Al) and the ScBe13 compound are in equilibrium with a beryllium solid solution (Be). Magnesium dissolves in both the aluminum component and the ScBe13 compound. The strengthening effect related to the decomposition of the solid solution and the precipitation of Al3Sc cannot be extended to the strengthening of ABM-type alloys. Additions of 0.1-0.15 wt % Sc only weakly improve the mechanical properties of the alloys due to the refinement of beryllium-component grains. At high scandium contents, the strength increases insignificantly due to primary precipitation of ScBe13 and the plasticity decreases simultaneously.

Scandium places aluminium welding on a new plateau

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

Irving, B.

1997-07-01

An interesting new development in nonferrous metallurgy seems to be taking the world by storm. The topic is scandium, a rare metal that is now being mined in the Ukraine. Known for its toughness, it was formerly a top secret material used in fighter planes, including the MIG 29, during the existence of the Soviet Union. This metal is now being introduced into a variety of aluminum alloys in this country, both in base metal and filler metal forms. The results are increases in strength, fatigue life and weldability. US interest in scandium-containing products is burgeoning, examples include aircraft, componentsmore » for automobiles and trucks, high-speed trains, and boats. The technology is being developed and implemented at two laboratories, one in Baltimore, MD, and the other in Kiev, Ukraine. Both laboratories belong to Ashurst Technology Ltd., Hamilton, Bermuda. The author recently visited the Baltimore laboratory where he learned more about scandium and its current and potential effects on industry. This report documents what he learned.« less

Scandium oxide antireflection coatings for superluminescent LEDs

NASA Technical Reports Server (NTRS)

Ladany, I.; Zanzucchi, P. J.; Andrews, J. T.; Kane, J.; Depiano, E.

1986-01-01

For an employment of laser diodes as superluminescent LEDs (SLDs) or amplifiers, the facets of the diodes must be coated with antireflection films. In the work reported, scandium oxide was evaporated from an e-beam source onto Supersil II fused silica substrates. The obtained samples were used for measurements of absorption and reflectivity. Results of index measurements on e-beam evaporated films are presented. It is shown that excellent coatings with reflectivities of 0.00025 can be obtained using these films. Attention is given to the refractive indices for scandium oxide films as a function of wavelength, the power output vs current for laser before coating and after coating with Sc2O3.

Study of strength properties of semi-finished products from economically alloyed high-strength aluminium-scandium alloys for application in automobile transport and shipbuilding

NASA Astrophysics Data System (ADS)

Baranov, Vladimir; Sidelnikov, Sergey; Zenkin, Evgeny; Frolov, Viktor; Voroshilov, Denis; Yakivyuk, Olga; Konstantinov, Igor; Sokolov, Ruslan; Belokonova, Irina

2018-04-01

The results of a study on the strength of rolled products from aluminium alloys doped with scandium under various processing conditions of hot and cold rolling are presented. The regularities of metal flow and the level of strength of deformed semi-finished products from aluminum-scandium alloys are established, depending on the total degree of deformation and the various modes of single reduction during rolling. It is shown that when using one heating of a cast billet to obtain high-quality semi-finished products, the temperature during the rolling process should not be lower than 350-370°, and the total degree of deformation does not exceed 50-60%. It was found that the semi-finished products from alloys with a content of scandium in the range 0.11-0.12% in the deformed state had elevated values of ultimate tensile strength and yield strength of the metal, which allows them to be recommended for industrial production of sheet metal products.

Structural properties of scandium inorganic salts

DOE PAGES

Sears, Jeremiah M.; Boyle, Timothy J.

2016-12-16

Here, the structural properties of reported inorganic scandium (Sc) salts were reviewed, including the halide (Cl, Br, and I), nitrate, sulfate, and phosphate salts. Additional analytical techniques used for characterization of these complexes (metrical data, FTIR and 45Sc NMR spectroscopy) were tabulated. A structural comparison of Sc to select lanthanide (La, Gd, Lu) salt complexes was briefly evaluated.

Highly Reactive Scandium Phosphinoalkylidene Complex: C-H and H-H Bonds Activation.

PubMed

Mao, Weiqing; Xiang, Li; Alvarez Lamsfus, Carlos; Maron, Laurent; Leng, Xuebing; Chen, Yaofeng

2017-01-25

The first scandium phosphinoalkylidene complex was synthesized and structurally characterized. The complex has the shortest Sc-C bond lengths reported to date (2.089(3) Å). DFT calculations reveal the presence of a three center π interaction in the complex. This scandium phosphinoalkylidene complex undergoes intermolecular C-H bond activation of pyridine, 4-dimethylamino pyridine and 1,3-dimethylpyrazole at room temperature. Furthermore, the complex rapidly activates H 2 under mild conditions. DFT calculations also demonstrate that the C-H activation of 1,3-dimethylpyrazole is selective for thermodynamic reasons and the relatively slow reaction is due to the need of fully breaking the chelating effect of the phosphino group to undergo the reaction whereas this is not the case for H 2 .

Lifetime measurements and oscillator strengths in singly ionized scandium and the solar abundance of scandium

NASA Astrophysics Data System (ADS)

Pehlivan Rhodin, A.; Belmonte, M. T.; Engström, L.; Lundberg, H.; Nilsson, H.; Hartman, H.; Pickering, J. C.; Clear, C.; Quinet, P.; Fivet, V.; Palmeri, P.

2017-12-01

The lifetimes of 17 even-parity levels (3d5s, 3d4d, 3d6s and 4p2) in the region 57 743-77 837 cm-1 of singly ionized scandium (Sc II) were measured by two-step time-resolved laser induced fluorescence spectroscopy. Oscillator strengths of 57 lines from these highly excited upper levels were derived using a hollow cathode discharge lamp and a Fourier transform spectrometer. In addition, Hartree-Fock calculations where both the main relativistic and core-polarization effects were taken into account were carried out for both low- and high-excitation levels. There is a good agreement for most of the lines between our calculated branching fractions and the measurements of Lawler & Dakin in the region 9000-45 000 cm-1 for low excitation levels and with our measurements for high excitation levels in the region 23 500-63 100 cm-1. This, in turn, allowed us to combine the calculated branching fractions with the available experimental lifetimes to determine semi-empirical oscillator strengths for a set of 380 E1 transitions in Sc II. These oscillator strengths include the weak lines that were used previously to derive the solar abundance of scandium. The solar abundance of scandium is now estimated to logε⊙ = 3.04 ± 0.13 using these semi-empirical oscillator strengths to shift the values determined by Scott et al. The new estimated abundance value is in agreement with the meteoritic value (logεmet = 3.05 ± 0.02) of Lodders, Palme & Gail.

Tunable and mode-locked laser action of Cr4+ in codoped forsterite Cr, Sc:Mg2SiO4

NASA Astrophysics Data System (ADS)

Sanina, V. V.; Mitrokhin, V. P.; Subbotin, K. A.; Lis, D. A.; Lis, O. N.; Ivanov, A. A.; Zharikov, E. V.

2018-01-01

The laser oscillation of tetravalent chromium and scandium codoped forsterite Cr4+,Sc:Mg2SiO4 single crystal has been demonstrated for the first time for continuous wave, tunable and mode-locked regimes. For comparison, the laser experiments have also been performed in the same configuration with the reference forsterite single crystal solely doped by chromium. The aim of scandium codoping is to inhibit the formation of parasitic trivalent chromium in the crystal. The crystal with scandium demonstrates a wider tuning range, lower lasing threshold and wider mode-locked lasing spectrum than those of the reference crystal, although the total lasing efficiency achieved by both crystals is nearly the same. The obtained results are discussed.

Ultrafast X-Ray Diffraction Studies of the Phase Transitions and Equation of State of Scandium Shock Compressed to 82 GPa

DOE PAGES

Briggs, R.; Gorman, M. G.; Coleman, A. L.; ...

2017-01-09

Using x-ray diffraction at the Linac Coherent Light Source x-ray free-electron laser, we have determined simultaneously and self-consistently the phase transitions and equation of state (EOS) of the lightest transition metal, scandium, under shock compression. On compression scandium undergoes a structural phase transition between 32 and 35 GPa to the same bcc structure seen at high temperatures at ambient pressures, and then a further transition at 46 GPa to the incommensurate host-guest polymorph found above 21 GPa in static compression at room temperature. Furthermore, shock melting of the host-guest phase is observed between 53 and 72 GPa with the disappearancemore » of Bragg scattering and the growth of a broad asymmetric diffraction peak from the high-density liquid.« less

Ultrafast X-Ray Diffraction Studies of the Phase Transitions and Equation of State of Scandium Shock Compressed to 82 GPa.

PubMed

Briggs, R; Gorman, M G; Coleman, A L; McWilliams, R S; McBride, E E; McGonegle, D; Wark, J S; Peacock, L; Rothman, S; Macleod, S G; Bolme, C A; Gleason, A E; Collins, G W; Eggert, J H; Fratanduono, D E; Smith, R F; Galtier, E; Granados, E; Lee, H J; Nagler, B; Nam, I; Xing, Z; McMahon, M I

2017-01-13

Using x-ray diffraction at the Linac Coherent Light Source x-ray free-electron laser, we have determined simultaneously and self-consistently the phase transitions and equation of state (EOS) of the lightest transition metal, scandium, under shock compression. On compression scandium undergoes a structural phase transition between 32 and 35 GPa to the same bcc structure seen at high temperatures at ambient pressures, and then a further transition at 46 GPa to the incommensurate host-guest polymorph found above 21 GPa in static compression at room temperature. Shock melting of the host-guest phase is observed between 53 and 72 GPa with the disappearance of Bragg scattering and the growth of a broad asymmetric diffraction peak from the high-density liquid.

The interactions between the sterically demanding trimesitylphosphine oxide and trimesityphosphine with scandium and selected lanthanide ions

NASA Astrophysics Data System (ADS)

Platt, Andrew W. G.; Singh, Kuldip

2016-05-01

The reactions between lanthanide nitrates, Ln(NO3)3 and scandium and lanthanide trifluoromethane sulfonates, Ln(Tf)3 with trimesitylphosphine oxide, Mes3PO show that coordination to the metal ions does not lead to crystalline complexes. Investigation of the reactions by 31-P NMR spectroscopy shows that weak complexes are formed in solution. The crystal structures of Mes3PO·0.5CH3CN (1) and [Mes3PO]3H3O·2CH3CN·Tf (2), formed in the reaction between ScTf3 and Mes3PO, are reported. Trimesitylphosphine, Mes3P, is protonated by scandium and lanthanide trifluoromethane sulfonates and lanthanide nitrates in CD3CN and the structure of [Mes3PH]Cl·HCl·2H2O (3) is reported.

Miniature High Density Scandate Cathodes for Linear Beam Devices

DTIC Science & Technology

2008-07-14

oxalic acid is added and nanoparticles of scandia precipitate out. We were successful with this process. 2.3 Experimental Method Measurement...process. The scandium oxide doped porous matrix is subsequently impregnated in the molten phase with 4:1:1 barium calcium aluminates to form the...scandium nitrate dissolved in pure alcohol using oxalic acid dehydrate as the precipitant. E-beam has successfully used this process to produce a

Rare earths, the lanthanides, yttrium and scandium

USGS Publications Warehouse

Bedinger, G.; Bleiwas, D.

2012-01-01

In 2011, rare earths were recovered from bastnasite concentrates at the Mountain Pass Mine in California. Consumption of refined rare-earth products decreased in 2011 from 2010. U.S. rare-earth imports originated primarily from China, with lesser amounts from Austria, Estonia, France and Japan. The United States imported all of its demand for yttrium metal and yttrium compounds, with most of it originating from China. Scandium was imported in various forms and processed domestically.

Synthesis, structures, and electroluminescent properties of scandium N,O-chelated complexes toward near-white organic light-emitting diodes.

PubMed

Katkova, Marina A; Balashova, Tatyana V; Ilichev, Vasilii A; Konev, Alexey N; Isachenkov, Nikolai A; Fukin, Georgy K; Ketkov, Sergey Yu; Bochkarev, Mikhail N

2010-06-07

Three members of a new class of electroluminescent, neutral, and monomeric scandium N,O-chelate complexes, namely, Sc(III)-tris-2-(2-benzoimidazol-2-yl)phenolate (1), Sc(III)-tris-2-(2-benzoxyazol-2-yl)phenolate (2), and Sc(III)-tris-2-(2-benzothiazol-2-yl)phenolate (3), have been prepared and X-ray characterized. DFT calculations have been performed. In contrast to the most frequently applied dual or multiple dopants in multilayer white OLED devices, all our simpler devices with the configuration of indium tin oxide/N,N'-bis(3-methylphenyl)-N,N'-diphenylbenzidine/neat scandium complex/Yb exhibit close to near-white emission with a blue hue (CIE(x,y) = 0.2147, 0.2379) in the case of 1, a cyan hue (0.2702, 0.3524) in the case of 2, and a yellowish hue (0.3468; 0.4284) in the case of 3.

Removal of acidic or basic α-amino acids in water by poorly water soluble scandium complexes.

PubMed

Hayashi, Nobuyuki; Jin, Shigeki; Ujihara, Tomomi

2012-11-02

To recognize α-amino acids with highly polar side chains in water, poorly water soluble scandium complexes with both Lewis acidic and basic portions were synthesized as artificial receptors. A suspension of some of these receptor molecules in an α-amino acid solution could remove acidic and basic α-amino acids from the solution. The compound most efficient at preferentially removing basic α-amino acids (arginine, histidine, and lysine) was the receptor with 7,7'-[1,3-phenylenebis(carbonylimino)]bis(2-naphthalenesulfonate) as the ligand. The neutral α-amino acids were barely removed by these receptors. Removal experiments using a mixed amino acid solution generally gave results similar to those obtained using solutions containing a single amino acid. The results demonstrated that the scandium complex receptors were useful for binding acidic and basic α-amino acids.

Surface studies on scandate cathodes and synthesized scandates

NASA Technical Reports Server (NTRS)

Lesny, Gary; Forman, Ralph

1990-01-01

Auger, ESCA, electron emission, evaporation, and desorption measurements were made on three different types of scandate surfaces. They are: (1) an impregnated top layer scandate cathode, (2) an unimpregnated top layer scandate cathode with a deposited barium or barium oxide adsorbate surface layer, and (3) a synthesized scandate surface, which replicates a scandate cathode surface. The purpose of these experiments was to determine the role that Sc2O3 plays in making the scandate cathode a more copious electron emitter than the conventional impregnated-type cathode. The synthesized scandate surface experiments consisted of depositing multilayer scandium on a tungsten surface, oxidizing the scandium, and then depositing either Ba or BaO on the scandium oxide surface. The results of these measurements showed that the low work function portions of the thin-film scandate cathode are where the Sc2O3 is the substrate and BaO is the adsorbate.

Current German Laser and Quantum Optics Research Reviewed at the 50th Annual Meeting of the Physikalische Gesellschaft.

DTIC Science & Technology

1986-04-23

Physics, Munster In the area of generating useable University) studied an interesting de- coherent high-frequency radiation, I vice, a silicon Fabry ...has a substantial crys- tingen) described studies with Cr- plus tal growing capability. One paper from Nd-doped gadolinium -scandium-gallium the Hamburg...institute, read by J. Drube, garnets (GSGG), and also with Cr-doped reported on Xe-flashlamp-pumped Cr:CSA(; % gadolinium -scandium-aluminum garnets

Crystallography, Spectroscopic Analysis, and Lasing Properties of Nd(3+) :Y3Sc2Al3O12

DTIC Science & Technology

1989-12-01

aluminum garnet (GSAG), are formed from more stable constitu- ent oxides than gallium-containing materials, 2. Experimental Results and such as gadolinium ...the which an assessment can be made regarding aluminum -based systems, such as YAG, YSAG, Nd:YSAG as a laser material. or gadolinium scandium...Structure oxidation state variation or oxygen vacancies, and this problem is greatly reduced in alumi- Yttrium scandium aluminum garnet be- nate systems

Enhancing Magnetic Functionality with Scandium: Breaking Stereotypes in the Design of Rare Earth Materials

DOE PAGES

Mudryk, Yaroslav; Paudyal, Durga; Liu, Jing; ...

2017-04-11

Replacement of strongly magnetic gadolinium with weakly magnetic scandium unexpectedly enhances ferromagnetic interactions in (Gd 1–xSc x) 5Ge 4. Based upon this counterintuitive experimental finding we demonstrate the unique role 3d 1 electrons of scandium atoms play in mediating magnetic interactions between the gadolinium atoms from the neighboring layers in the Sm 5Ge 4-type crystal lattice. Scandium substitutions at and below 20% rapidly increase the Curie temperature, TC, of the Gd 5Ge 4 parent, eliminate both the kinetic arrest and hysteresis, and drastically improve reversibility of the first-order magnetostructural transformation at T C. In agreement with first-principles predictions, higher thanmore » 20% Sc leads to the formation of a closely related Pu 5Rh 4-type structure where the first-order magnetostructural transformation is replaced by a conventional second-order ferromagnetic ordering that remains accompanied by a continuous rearrangement of the crystal lattice. In conclusion, comparison of two materials with similar structures and compositions shows that significantly stronger magnetocaloric effect occurs in the first-order material, which also shows very small hysteresis. Furthermore, we demonstrate that a behavior of a specific interatomic distance can predict anomalous physical properties in a series of alloys where compositional dependence of lattice parameters suggests a rather trivial solid solubility and uninteresting magnetism.« less

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.

A crystalline anionic complex of scandium nitride endometallofullerene: experimental observation of single-bonded (Sc3N@Ih-C80−)2 dimers†

PubMed Central

Konarev, Dmitri V.; Zorina, Leokadiya V.; Khasanov, Salavat S.; Popov, Alexey A.; Otsuka, Akihiro; Yamochi, Hideki; Saito, Gunzi; Lyubovskaya, Rimma N.

2017-01-01

Reduction of scandium nitride clusterfullerene, Sc3N@Ih-C80, by sodium fluorenone ketyl in the presence of cryptand[2,2,2] allows the crystallization of the {cryptand[2,2,2](Na+)}2(Sc3N@Ih-C80−)2·2.5C6H4Cl2 (1) salt. The Sc3N@Ih-C80•− radical anions are dimerized to form single-bonded (Sc3N@Ih-C80−)2 dimers. PMID:27511304

Rare-Earth Ion-Host Lattice Interactions: 15. Analysis of the Spectra of Nd3+ in Gd3Sc2Ga3O12.

DTIC Science & Technology

1984-05-01

Luminescence of Cr3+ Ions in Gadolinium Gallium and Gadolinium Scandium Gallium Garnet CT’stals, Soy. J. Quant. Electron. 12 (1982), 1124. 6M. Dutoit, J. C...Shcherbakov, Absolute Quantum Efficiency of the Luminescence of Cr3+ Ions in Gadolinium Gallium and Gadolinium Scandium Gallium Garnet Crystals, Soy. J...HDL Project: 324332 19. KEY WORDS (Continue on reverse side it necessary end Identify by block number) Rare earth Mixed garnet Spectra Laser Judd-Ofelt

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.

On the Possibility of using Alluminium-Magnesium Alloys with Improved Mechanical Characteristics for Body Elements of Zenit-2S Launch Vehicle Propellant Tanks

NASA Astrophysics Data System (ADS)

Sitalo, V.; Lytvyshko, T.

2002-01-01

Yuzhnoye SDO developed several generations of launch vehicles and spacecraft that are characterized by weight perfection, optimal cost, accuracy of output geometrical characteristics, stable strength characteristics, high tightness. The main structural material of launch vehicles are thermally welded non-strengthened aluminium- magnesium alloys. The aluminium-magnesium alloys in the annealed state have insufficiently high strength characteristics. Considerable increase of yield strength of sheets and plates can be reached by cold working but in this case, plasticity reduces. An effective way to improve strength of aluminium-magnesium alloys is their alloying with scandium. The alloying with scandium leads to modification of the structure of ingots (size reduction of cast grain) and formation of supersaturated solid solutions of scandium and aluminium during crystallization. During subsequent heatings (annealing of the ingots, heating for deformation) the solid solution disintegrates with the formation of disperse particles of Al3Sc type, that cause great strengthening of the alloy. High degree of dispersion and density of distribution in the matrix of secondary Al3Sc particles contribute to the considerable increase of the temperature of recrystallization of deformed intermediate products and to the formation of stable non-recrystallized structure. The alloying of alluminium-magnesium alloys with scandium increases their strength and operational characteristics, preserves their technological and corrosion properties, improves weldability. The alloys can be used within the temperature limits ­196-/+150 0C. The experimental structures of propellant tanks made of alluminium-magnesium alloys with scandium have been manufactured and tested. It was ascertained that the propellant tanks have higher margin of safety during loading with internal pressure and higher stability factor of the shrouds during loading with axial compression force which is caused by higher value of yield strength. The analysis of the performed work showed good prospects of using the alluminium-magnesium alloys with increased mechanical characteristics for making body elements of propellant tanks of the Zenit -2S launch vehicles. The use of these alloys can give the increase of structural strength by 20-30% and considerable increase of payload weight.

Arctic Deep Water Ferromanganese-Oxide Deposits Reflect the Unique Characteristics of the Arctic Ocean

NASA Astrophysics Data System (ADS)

Hein, James R.; Konstantinova, Natalia; Mikesell, Mariah; Mizell, Kira; Fitzsimmons, Jessica N.; Lam, Phoebe J.; Jensen, Laramie T.; Xiang, Yang; Gartman, Amy; Cherkashov, Georgy; Hutchinson, Deborah R.; Till, Claire P.

2017-11-01

Little is known about marine mineral deposits in the Arctic Ocean, an ocean dominated by continental shelf and basins semi-closed to deep-water circulation. Here, we present data for ferromanganese crusts and nodules collected from the Amerasia Arctic Ocean in 2008, 2009, and 2012 (HLY0805, HLY0905, and HLY1202). We determined mineral and chemical compositions of the crusts and nodules and the onset of their formation. Water column samples from the GEOTRACES program were analyzed for dissolved and particulate scandium concentrations, an element uniquely enriched in these deposits. The Arctic crusts and nodules are characterized by unique mineral and chemical compositions with atypically high growth rates, detrital contents, Fe/Mn ratios, and low Si/Al ratios, compared to deposits found elsewhere. High detritus reflects erosion of submarine outcrops and North America and Siberia cratons, transport by rivers and glaciers to the sea, and distribution by sea ice, brines, and currents. Uniquely high Fe/Mn ratios are attributed to expansive continental shelves, where diagenetic cycling releases Fe to bottom waters, and density flows transport shelf bottom water to the open Arctic Ocean. Low Mn contents reflect the lack of a mid-water oxygen minimum zone that would act as a reservoir for dissolved Mn. The potential host phases and sources for elements with uniquely high contents are discussed with an emphasis on scandium. Scandium sorption onto Fe oxyhydroxides and Sc-rich detritus account for atypically high scandium contents. The opening of Fram Strait in the Miocene and ventilation of the deep basins initiated Fe-Mn crust growth ˜15 Myr ago.

Arctic deep-water ferromanganese-oxide deposits reflect the unique characteristics of the Arctic Ocean

USGS Publications Warehouse

Hein, James; Konstantinova, Natalia; Mikesell, Mariah; Mizell, Kira; Fitzsimmons, Jessica N.; Lam, Phoebe; Jensen, Laramie T.; Xiang, Yang; Gartman, Amy; Cherkashov, Georgy; Hutchinson, Deborah; Till, Claire P.

2017-01-01

Little is known about marine mineral deposits in the Arctic Ocean, an ocean dominated by continental shelf and basins semi-closed to deep-water circulation. Here, we present data for ferromanganese crusts and nodules collected from the Amerasia Arctic Ocean in 2008, 2009, and 2012 (HLY0805, HLY0905, HLY1202). We determined mineral and chemical compositions of the crusts and nodules and the onset of their formation. Water column samples from the GEOTRACES program were analyzed for dissolved and particulate scandium concentrations, an element uniquely enriched in these deposits.The Arctic crusts and nodules are characterized by unique mineral and chemical compositions with atypically high growth rates, detrital contents, Fe/Mn ratios, and low Si/Al ratios, compared to deposits found elsewhere. High detritus reflects erosion of submarine outcrops and North America and Siberia cratons, transport by rivers and glaciers to the sea, and distribution by sea ice, brines, and currents. Uniquely high Fe/Mn ratios are attributed to expansive continental shelves, where diagenetic cycling releases Fe to bottom waters, and density flows transport shelf bottom water to the open Arctic Ocean. Low Mn contents reflect the lack of a mid-water oxygen minimum zone that would act as a reservoir for dissolved Mn. The potential host phases and sources for elements with uniquely high contents are discussed with an emphasis on scandium. Scandium sorption onto Fe oxyhydroxides and Sc-rich detritus account for atypically high scandium contents. The opening of Fram Strait in the Miocene and ventilation of the deep basins initiated Fe-Mn crust growth ∼15 Myr ago.

The Oxidation Products of Aluminum Hydride and Boron Aluminum Hydride Clusters

DTIC Science & Technology

2016-01-04

AFRL-AFOSR-VA-TR-2016-0075 The Oxidation Products of Aluminum Hydride and Boron Aluminum Hydride Clusters KIT BOWEN JOHNS HOPKINS UNIV BALTIMORE MD...Hydride and Boron Aluminum Hydride Clusters 5a.  CONTRACT NUMBER 5b.  GRANT NUMBER FA9550-14-1-0324 5c.  PROGRAM ELEMENT NUMBER 61102F 6. AUTHOR(S) KIT...of both Aluminum Hydride Cluster Anions and Boron Aluminum Hydride Cluster Anions with Oxygen: Anionic Products The anionic products of reactions

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.

Separation of 44Ti from proton irradiated scandium by using solid-phase extraction chromatography and design of 44Ti/44Sc generator system.

PubMed

Radchenko, V; Meyer, C A L; Engle, J W; Naranjo, C M; Unc, G A; Mastren, T; Brugh, M; Birnbaum, E R; John, K D; Nortier, F M; Fassbender, M E

2016-12-16

Scandium-44g (half-life 3.97h [1]) shows promise for positron emission tomography (PET) imaging of longer biological processes than that of the current gold standard, 18 F, due to its favorable decay parameters. One source of 44g Sc is the long-lived parent nuclide 44 Ti (half-life 60.0 a). A 44 Ti/ 44g Sc generator would have the ability to provide radionuclidically pure 44g Sc on a daily basis. The production of 44 Ti via the 45 Sc(p,2n) reaction requires high proton beam currents and long irradiation times. Recovery and purification of no-carrier added (nca) 44 Ti from scandium metal targets involves complex separation chemistry. In this study, separation systems based on solid phase extraction chromatography were investigated, including branched diglycolamide (BDGA) resin and hydroxamate based ZR resin. Results indicate that ZR resin in HCl media represents an effective 44 Ti/ 44g Sc separation system. Copyright © 2016 Elsevier B.V. All rights reserved.

Separation of 44Ti from proton irradiated scandium by using solid-phase extraction chromatography and design of 44Ti/ 44Sc generator system

DOE PAGES

Radchenko, Valery; Meyer, Catherine Anne Louise; Engle, Jonathan Ward; ...

2016-11-24

Scandium-44 g (half-life 3.97 h) shows promise for positron emission tomography (PET) imaging of longer biological processes than that of the current gold standard, 18F, due to its favorable decay parameters. One source of 44gSc is the long-lived parent nuclide 44Ti (half-life 60.0 a). A 44Ti/ 44gSc generator would have the ability to provide radionuclidically pure 44gSc on a daily basis. The production of 44Ti via the 45Sc(p,2n) reaction requires high proton beam currents and long irradiation times. Recovery and purification of no-carrier added (nca) 44Ti from scandium metal targets involves complex separation chemistry. In this study, separation systems basedmore » on solid phase extraction chromatography were investigated, including branched diglycolamide (BDGA) resin and hydroxamate based ZR resin. Lastly, results indicate that ZR resin in HCl media represents an effective 44Ti/ 44gSc separation system.« less

Change of the arc attachment mode and its effect on the lifetime in automotive high intensity discharge lamps

NASA Astrophysics Data System (ADS)

Alexejev, Alexander; Flesch, Peter; Mentel, Jürgen; Awakowicz, Peter

2016-10-01

In modern cars, the new generation Hg-free high intensity discharge (HID) lamps, the so called xenon lamps, take an important role. The long lifetime of these lamps is achieved by doping the tungsten electrodes with thorium. Thorium forms a dipole layer on the electrode surface, thus reducing the work function of tungsten. However, thoriating the electrodes is also an issue of trade and transport regulation, so a substitute is looked into. This work shows the influence of the arc attachment mode on the lifetime of the lamps. The mode of the arc attachment changes during the run-up phase of automotive HID lamps after a characteristic time period depending, i.e., on the filling of the lamps, which is dominated by scandium. It will be shown that this characteristic time period for the change of the attachment mode determines the long term performance of Hg-free xenon lamps. Measurements attributing the mode change to the scandium density in the filling are presented. The emitter effect of scandium will be suggested to be the reason of the mode change.

Fundamental experiments on hydride reorientation in zircaloy

NASA Astrophysics Data System (ADS)

Colas, Kimberly B.

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

Betavoltaics using scandium tritide and contact potential difference

NASA Astrophysics Data System (ADS)

Liu, Baojun; Chen, Kevin P.; Kherani, Nazir P.; Zukotynski, Stefan; Antoniazzi, Armando B.

2008-02-01

Tritium-powered betavoltaic micropower sources using contact potential difference (CPD) are demonstrated. Thermally stable scandium tritide thin films with a surface activity of 15mCi/cm2 were used as the beta particle source. The electrical field created by the work function difference between the ScT film and a platinum or copper electrode was used to separate the beta-generated electrical charge carriers. Open circuit voltages of 0.5 and 0.16V and short circuit current densities of 2.7 and 5.3nA/cm2 were achieved for gaseous and solid dielectric media-based CPD cells, respectively.

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.

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.

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.

Scandium(III) complexes of monophosphorus acid DOTA analogues: a thermodynamic and radiolabelling study with (44)Sc from cyclotron and from a (44)Ti/(44)Sc generator.

PubMed

Kerdjoudj, R; Pniok, M; Alliot, C; Kubíček, V; Havlíčková, J; Rösch, F; Hermann, P; Huclier-Markai, S

2016-01-28

The complexation ability of DOTA analogs bearing one methylenephosphonic (DO3AP) or methylenephosphinic (DO3AP(PrA) and DO3AP(ABn)) acid pendant arm toward scandium was evaluated. Stability constants of their scandium(iii) complexes were determined by potentiometry combined with (45)Sc NMR spectroscopy. The stability constants of the monophosphinate analogues are somewhat lower than that of the Sc-DOTA complex. The phosphorus acid moiety interacts with trivalent scandium even in very acidic solutions forming out-of-cage complexes; the strong affinity of the phosphonate group to Sc(iii) precludes stability constant determination of the Sc-DO3AP complex. These results were compared with those obtained by the free-ion selective radiotracer extraction (FISRE) method which is suitable for trace concentrations. FISRE underestimated the stability constants but their relative order was preserved. Nonetheless, as this method is experimentally simple, it is suitable for a quick relative comparison of stability constant values under trace concentrations. Radiolabelling of the ligands with (44)Sc was performed using the radioisotope from two sources, a (44)Ti/(44)Sc generator and (44m)Sc/(44)Sc from a cyclotron. The best radiolabelling conditions for the ligands were pH = 4, 70 °C and 20 min which were, however, not superior to those of the parent DOTA. Nonetheless, in vitro behaviour of the Sc(iii) complexes in the presence of hydroxyapatite and rat serum showed sufficient stability of (44)Sc complexes of these ligands for in vivo applications. PET images and ex vivo biodistribution of the (44)Sc-DO3AP complex performed on healthy Wistar male rats showed no specific bone uptake and rapid clearance through urine.

Interaction of scandium and titanium atoms with a carbon surface containing five- and seven-membered rings

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

Krasnov, P. O., E-mail: kpo1980@gmail.com; Eliseeva, N. S.; Kuzubov, A. A., E-mail: alex_xx@rambler.ru

2012-01-15

The use of carbon nanotubes coated by atoms of transition metals to store molecular hydrogen is associated with the problem of the aggregation of these atoms, which leads to the formation of metal clusters. The quantum-chemical simulation of cluster models of the carbon surface of a graphene type with scandium and titanium atoms has been performed. It has been shown that the presence of five- and seven-membered rings, in addition to six-membered rings, in these structures makes it possible to strongly suppress the processes of the migration of metal atoms over the surface, preventing their clustering.

Rare earths, the lanthanides, yttrium and scandium

USGS Publications Warehouse

Hedrick, J.B.

2006-01-01

In 2005, rare earths were not mined in the United States. The major supplier, Molycorp, continued to maintain a large stockpile of rare-earth concentrates and compounds. Consumption decreased of refined rare-earth products. The United States remained a major importer and exporter of rare earths in 2005. During the same period, yttrium was not mined or refined in the US. Hence, supply of yttrium compounds for refined yttrium products came from China, France and Japan. Scandium was not also mined. World production was primarily in China, Russia and Ukraine. Demand for rare earths in 2006 is expected to be closely tied to economic conditions in the US.

Static high pressure studies on Nd and Sc

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

Akella, J.; Xu, J.; Smith, G.S.

1985-06-24

We have investigated the crystal structural transformations in neodymium and scandium up to 4.0 GPa pressure and at room temperature, in a diamond-anvil high pressure apparatus. Nd has a double hexagonal-close packed (dhcp) structure at ambient pressure and temperature. Then it transforms to a face-centered cubic (fcc) structure at 3.8 GPa, which further transforms to a triple hexagonal-close packed structure (thcp) at about 18.0 GPa. In scandium we observed only one transformation from the hexagonal-close packed (hcp) structure at room temperature to a tetragonal structure. This transformation occurs between 19.0 and 23.2 GPa pressure.

Energy levels, oscillator strengths, and transition probabilities for sulfur-like scandium, Sc VI

NASA Astrophysics Data System (ADS)

El-Maaref, A. A.; Abou Halaka, M. M.; Saddeek, Yasser B.

2017-09-01

Energy levels, Oscillator strengths, and transition probabilities for sulfur-like scandium are calculated using CIV3 code. The calculations have been executed in an intermediate coupling scheme using Breit-Pauli Hamiltonian. The present calculations have been compared with the experimental data and other theoretical calculations. LANL code has been used to confirm the accuracy of the present calculations, where the calculations using CIV3 code agree well with the corresponding values by LANL code. The calculated energy levels and oscillator strengths are in reasonable agreement with the published experimental data and theoretical values. We have calculated lifetimes of some excited levels, as well.

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(+).

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

Major- and Trace-Element Concentrations in Soils from Two Geochemical Surveys (1972 and 2005) of the Denver, Colorado, Metropolitan Area

USGS Publications Warehouse

Kilburn, James E.; Smith, David B.; Closs, L. Graham; Smith, Steven M.

2007-01-01

Introduction This report contains major- and trace-element concentration data for soil samples collected in 1972 and 2005 from the Denver, Colorado, metropolitan area. A total of 405 sites were sampled in the 1972 study from an area approximately bounded by the suburbs of Golden, Thornton, Aurora, and Littleton to the west, north, east, and south, respectively. This data set included 34 duplicate samples collected in the immediate vicinity of the primary sample. In 2005, a total of 464 sites together with 34 duplicates were sampled from the same approximate localities sampled in 1972 as well as additional sites in east Aurora and the area surrounding the Rocky Mountain Arsenal. Sample density for both surveys was on the order of 1 site per square mile. At each site, sample material was collected from a depth of 0-5 inches. Each sample collected was analyzed for near-total major- and trace-element composition by the following methods: (1) inductively coupled plasma-mass spectrometry (ICP-MS) and inductively coupled plasma-atomic emission spectrometry (ICP-AES) for aluminum, antimony, arsenic, barium, beryllium, bismuth, cadmium, calcium, cerium, cesium, chromium, cobalt, copper, gallium, indium, iron, lanthanum, lead, lithium, magnesium, manganese, molybdenum, nickel, niobium, phosphorus, potassium, rubidium, scandium, silver, sodium, strontium, sulfur, tellurium, thallium, thorium, tin, titanium, tungsten, uranium, vanadium, yttrium, and zinc; and (2) hydride generation-atomic absorption spectrometry for selenium. The samples collected in 2005 were also analyzed by a cold vapor-atomic absorption method for mercury. This report makes available the analytical results of these studies.

Boron hydride polymer coated substrates

DOEpatents

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

1986-08-27

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

Boron hydride polymer coated substrates

DOEpatents

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

1987-01-01

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

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.

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

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

Tensile properties of titanium electrolytically charged with hydrogen

NASA Technical Reports Server (NTRS)

Smith, R. J.; Otterson, D. A.

1971-01-01

Yield strength, ultimate tensile strength, and elongation were studied for annealed titanium electrolytically charged with hydrogen. The hydrogen was present as a surface hydride layer. These tensile properties were generally lower for uncharged titanium than for titanium with a continuous surface hydride; they were greater for uncharged titanium than for titanium with an assumed discontinuous surface hydride. We suggest that the interface between titanium and titanium hydride is weak. And the hydride does not necessarily impair strength and ductility of annealed titanium. The possibility that oxygen and/or nitrogen can embrittle titanium hydride is discussed.

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.

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.

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.

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)

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

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

Determination of scandium in acid mine drainage by ICP-OES with flow injection on-line preconcentration using oxidized multiwalled carbon nanotubes.

PubMed

Jerez, Javier; Isaguirre, Andrea C; Bazán, Cristian; Martinez, Luis D; Cerutti, Soledad

2014-06-01

An on-line scandium preconcentration and determination system implemented with inductively coupled plasma optical emission spectrometry associated with flow injection was studied. Trace amounts of scandium were preconcentrated by sorption on a minicolumn packed with oxidized multiwalled carbon nanotubes, at pH 1.5. The retained analyte was removed from the minicolumn with 30% (v/v) nitric acid. A total enrichment factor of 225-fold was obtained within a preconcentration time of 300 s (for a 25 mL sample volume). The overall time required for preconcentration and elution of 25 mL of sample was about 6 min; the throughput was about 10 samples per hour. The value of the detection limit was 4 ng L(-1) and the precision for 10 replicate determinations at 100 ng L(-1) Sc level was 5% relative standard deviation, calculated from the peak heights obtained. The calibration graph using the preconcentration system was linear with a correlation coefficient of 0.9996 at levels near the detection limits up to at least 10 mg L(-1). After optimization, the method was successfully applied to the determination of Sc in an acid drainage from an abandoned mine located in the province of San Luis, Argentina. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

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.

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.

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

Autocatalytic formation of an iron(IV)-oxo complex via scandium ion-promoted radical chain autoxidation of an iron(II) complex with dioxygen and tetraphenylborate.

PubMed

Nishida, Yusuke; Lee, Yong-Min; Nam, Wonwoo; Fukuzumi, Shunichi

2014-06-04

A non-heme iron(IV)-oxo complex, [(TMC)Fe(IV)(O)](2+) (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), was formed by oxidation of an iron(II) complex ([(TMC)Fe(II)](2+)) with dioxygen (O2) and tetraphenylborate (BPh4(-)) in the presence of scandium triflate (Sc(OTf)3) in acetonitrile at 298 K via autocatalytic radical chain reactions rather than by a direct O2 activation pathway. The autocatalytic radical chain reaction is initiated by scandium ion-promoted electron transfer from BPh4(-) to [(TMC)Fe(IV)(O)](2+) to produce phenyl radical (Ph(•)). The chain propagation step is composed of the addition of O2 to Ph(•) and the reduction of the resulting phenylperoxyl radical (PhOO(•)) by scandium ion-promoted electron transfer from BPh4(-) to PhOO(•) to produce phenyl hydroperoxide (PhOOH), accompanied by regeneration of phenyl radical. PhOOH reacts with [(TMC)Fe(II)](2+) to yield phenol (PhOH) and [(TMC)Fe(IV)(O)](2+). Biphenyl (Ph-Ph) was formed via the radical chain autoxidation of BPh3 by O2. The induction period of the autocatalytic radical chain reactions was shortened by addition of a catalytic amount of [(TMC)Fe(IV)(O)](2+), whereas addition of a catalytic amount of ferrocene that can reduce [(TMC)Fe(IV)(O)](2+) resulted in elongation of the induction period. Radical chain autoxidation of BPh4(-) by O2 also occurred in the presence of Sc(OTf)3 without [(TMC)Fe(IV)(O)](2+), initiating the autocatalytic oxidation of [(TMC)Fe(II)](2+) with O2 and BPh4(-) to yield [(TMC)Fe(IV)(O)](2+). Thus, the general view for formation of non-heme iron(IV)-oxo complexes via O2-binding iron species (e.g., Fe(III)(O2(•-))) without contribution of autocatalytic radical chain reactions should be viewed with caution.

Effects of scandium substitution on the crystal structure and luminescence properties of LuBO{sub 3}: Ce{sup 3+}

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

Wu, Yuntao, E-mail: caswyt@hotmail.com; Ren, Guohao, E-mail: rgh@mail.sic.ac.cn; Ding, Dongzhou

2012-10-15

The calcite phase of LuBO{sub 3} and ScBO{sub 3} polycrystalline powders were synthesized by solid state reaction method, and the Lu{sub 1-x}Sc{sub x}BO{sub 3}:Ce (x=0.2, 0.5, 0.7) single crystals were grown by the Czochralski method. A large composition deviation between the initial polycrystalline powders and final single crystal was confirmed by electron probe micro-analysis. Raman spectroscopy revealed that moderate lattice disorder was induced by scandium substitution. However, based on the single crystal X-ray study, we finally concluded that the crystal structure of lutetium scandium orthoborate still crystallized in the rhombohedral system belonging to R3{sup -}c. Furthermore, the relationship between themore » energies of the five 5d levels of Ce{sup 3+} and the crystalline environment was revealed. The total redshift, total crystal field splitting, and centroid shift of Lu{sub 1-x}Sc{sub x}BO{sub 3}:Ce{sup 3+} were calculated based on their VUV excitation spectra. The variations trend of these observed spectroscopic parameters was in accordance with the predicted ones. - Graphical abstract: The crystal structure of Lu{sub 1-x}Sc{sub x}BO{sub 3}:Ce is rhombohedral system with R3{sup -}c space group. The relationship between the energies of the five Ce{sup 3+} 5d levels and the crystalline environment is established. Highlights: Black-Right-Pointing-Pointer Moderate lattice disorder is induced by scandium doping. Black-Right-Pointing-Pointer The crystal structure of Lu{sub 1-x}Sc{sub x}BO{sub 3}:Ce is rhombohedral system with R3{sup -}c space group. Black-Right-Pointing-Pointer Relationship between energies of Ce{sup 3+} 5d levels and crystalline environment is established. Black-Right-Pointing-Pointer The spectroscopic parameters are experimentally and theoretically calculated.« less

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

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.

Thermodynamic and kinetic study of scandium(III) complexes of DTPA and DOTA: a step toward scandium radiopharmaceuticals.

PubMed

Pniok, Miroslav; Kubíček, Vojtěch; Havlíčková, Jana; Kotek, Jan; Sabatie-Gogová, Andrea; Plutnar, Jan; Huclier-Markai, Sandrine; Hermann, Petr

2014-06-23

Diethylenetriamine-N,N,N',N'',N''-pentaacetic acid (DTPA) and 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) scandium(III) complexes were investigated in the solution and solid state. Three (45)Sc NMR spectroscopic references suitable for aqueous solutions were suggested: 0.1 M Sc(ClO4)3 in 1 M aq. HClO4 (δSc =0.0 ppm), 0.1 M ScCl3 in 1 M aq. HCl (δSc =1.75 ppm) and 0.01 M [Sc(ox)4](5-) (ox(2-) = oxalato) in 1 M aq. K2C2O4 (δSc =8.31 ppm). In solution, [Sc(dtpa)](2-) complex (δSc = 83 ppm, Δν = 770 Hz) has a rather symmetric ligand field unlike highly unsymmetrical donor atom arrangement in [Sc(dota)](-) anion (δSc = 100 ppm, Δν = 4300 Hz). The solid-state structure of K8[Sc2(ox)7]⋅13 H2O contains two [Sc(ox)3](3-) units bridged by twice "side-on" coordinated oxalate anion with Sc(3+) ion in a dodecahedral O8 arrangement. Structures of [Sc(dtpa)](2-) and [Sc(dota)](-) in [(Hguanidine)]2[Sc(dtpa)]⋅3 H2O and K[Sc(dota)][H6 dota]Cl2⋅4 H2O, respectively, are analogous to those of trivalent lanthanide complexes with the same ligands. The [Sc(dota)](-) unit exhibits twisted square-antiprismatic arrangement without an axial ligand (TSA' isomer) and [Sc(dota)](-) and (H6 dota)(2+) units are bridged by a K(+) cation. A surprisingly high value of the last DOTA dissociation constant (pKa =12.9) was determined by potentiometry and confirmed by using NMR spectroscopy. Stability constants of scandium(III) complexes (log KScL 27.43 and 30.79 for DTPA and DOTA, respectively) were determined from potentiometric and (45)Sc NMR spectroscopic data. Both complexes are fully formed even below pH 2. Complexation of DOTA with the Sc(3+) ion is much faster than with trivalent lanthanides. Proton-assisted decomplexation of the [Sc(dota)](-) complex (τ1/2 =45 h; 1 M aq. HCl, 25 °C) is much slower than that for [Ln(dota)](-) complexes. Therefore, DOTA and its derivatives seem to be very suitable ligands for scandium radioisotopes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Improving sensitivity and resolution of MQMAS spectra: A 45Sc-NMR case study of scandium sulphate pentahydrate

NASA Astrophysics Data System (ADS)

Chandran, C. Vinod; Cuny, Jérôme; Gautier, Régis; Pollès, Laurent Le; Pickard, Chris J.; Bräuniger, Thomas

2010-04-01

To efficiently obtain multiple-quantum magic-angle spinning (MQMAS) spectra of the nuclide 45Sc (I = 7/2), we have combined several previously suggested techniques to enhance the signal-to-noise ratio and to improve spectral resolution for the test sample, scandium sulphate pentahydrate (ScSPH). Whereas the 45Sc-3QMAS spectrum of ScSPH does not offer sufficient resolution to clearly distinguish between the 3 scandium sites present in the crystal structure, these sites are well-resolved in the 5QMAS spectrum. The loss of sensitivity incurred by using MQMAS with 5Q coherence order is partly compensated for by using fast-amplitude modulated (FAM) sequences to improve the efficiency of both 5Q coherence excitation and conversion. Also, heteronuclear decoupling is employed to minimise dephasing of the 45Sc signal during the 5Q evolution period due to dipolar couplings with the water protons in the ScSPH sample. Application of multi-pulse decoupling schemes such as TPPM and SPINAL results in improved sensitivity and resolution in the F1 (isotropic) dimension of the 5QMAS spectrum, the best results being achieved with the recently suggested SWf-TPPM sequence. By numerical fitting of the 45Sc-NMR spectra of ScSPH from 3QMAS, 5QMAS and single-quantum MAS at magnetic fields B0 = 9.4 T and 17.6 T, the isotropic chemical shift δiso, the quadrupolar coupling constant χ, and the asymmetry parameter η were obtained. Averaging over all experiments, the NMR parameters determined for the 3 scandium sites, designated (a), (b) and (c) are: δiso(a) = -15.5 ± 0.5 ppm, χ(a) = 5.60 ± 0.10 MHz, η(a) = 0.06 ± 0.05; δiso(b) = -12.9 ± 0.5 ppm, χ(b) = 4.50 ± 0.10 MHz, η(b) = 1.00 ± 0.00; and δiso(c) = -4.7 ± 0.2 ppm, χ(c) = 4.55 ± 0.05 MHz, η(c) = 0.50 ± 0.02. The NMR scandium species were assigned to the independent crystallographic sites by evaluating their experimental response to proton decoupling, and by density functional theory (DFT) calculations using the PAW and GIPAW approaches, in the following way: Sc(1) to (c), Sc(2) to (a), and Sc(3) to (b). The need to compute NMR parameters using an energy-optimised crystal structure is once again demonstrated.

Improving sensitivity and resolution of MQMAS spectra: a 45Sc-NMR case study of scandium sulphate pentahydrate.

PubMed

Chandran, C Vinod; Cuny, Jérôme; Gautier, Régis; Le Pollès, Laurent; Pickard, Chris J; Bräuniger, Thomas

2010-04-01

To efficiently obtain multiple-quantum magic-angle spinning (MQMAS) spectra of the nuclide 45Sc (I=7/2), we have combined several previously suggested techniques to enhance the signal-to-noise ratio and to improve spectral resolution for the test sample, scandium sulphate pentahydrate (ScSPH). Whereas the 45Sc-3QMAS spectrum of ScSPH does not offer sufficient resolution to clearly distinguish between the 3 scandium sites present in the crystal structure, these sites are well-resolved in the 5QMAS spectrum. The loss of sensitivity incurred by using MQMAS with 5Q coherence order is partly compensated for by using fast-amplitude modulated (FAM) sequences to improve the efficiency of both 5Q coherence excitation and conversion. Also, heteronuclear decoupling is employed to minimise dephasing of the 45Sc signal during the 5Q evolution period due to dipolar couplings with the water protons in the ScSPH sample. Application of multi-pulse decoupling schemes such as TPPM and SPINAL results in improved sensitivity and resolution in the F(1) (isotropic) dimension of the 5QMAS spectrum, the best results being achieved with the recently suggested SW(f)-TPPM sequence. By numerical fitting of the 45Sc-NMR spectra of ScSPH from 3QMAS, 5QMAS and single-quantum MAS at magnetic fields B(0)=9.4 T and 17.6 T, the isotropic chemical shift delta(iso), the quadrupolar coupling constant chi, and the asymmetry parameter eta were obtained. Averaging over all experiments, the NMR parameters determined for the 3 scandium sites, designated (a), (b) and (c) are: delta(iso)(a)=-15.5+/-0.5 ppm, chi(a)=5.60+/-0.10 MHz, eta(a)=0.06+/-0.05; delta(iso)(b)=-12.9+/-0.5 ppm, chi(b)=4.50+/-0.10 MHz, eta(b)=1.00+/-0.00; and delta(iso)(c)=-4.7+/-0.2 ppm, chi(c)=4.55+/-0.05 MHz, eta(c)=0.50+/-0.02. The NMR scandium species were assigned to the independent crystallographic sites by evaluating their experimental response to proton decoupling, and by density functional theory (DFT) calculations using the PAW and GIPAW approaches, in the following way: Sc(1) to (c), Sc(2) to (a), and Sc(3) to (b). The need to compute NMR parameters using an energy-optimised crystal structure is once again demonstrated. 2009 Elsevier Inc. All rights reserved.

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.

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

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 use in this application. The metal hydride component design tool developed in this work selects between metal hydride materials on an unprecedented scale. It can be easily applied to other hydrogen-based thermal systems, making it a powerful and versatile tool.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Method of producing a chemical hydride

DOEpatents

Klingler, Kerry M.; Zollinger, William T.; Wilding, Bruce M.; Bingham, Dennis N.; Wendt, Kraig M.

2007-11-13

A method of producing a chemical hydride is described and which includes selecting a composition having chemical bonds and which is capable of forming a chemical hydride; providing a source of a hydrocarbon; and reacting the composition with the source of the hydrocarbon to generate a chemical hydride.

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...

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

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

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 certainly serve as one of the most effective ways to estimate the new E values from ΔG(H(-)A)(R(+)) or vice versa. Combining the hydride affinities and the reduction potentials of the arylcarbeniums, we obtained the bond homolytic dissociation Gibbs free energy changes of the C-H bonds in the corresponding hydride adducts in acetonitrile, ΔG(HD)(RH), and found that the effects of the substituent on ΔG(HD)(RH) are very small. Simple thermodynamic analytic platforms for the three C-H cleavage modes were constructed. It is evident that the present work would be helpful in understanding the nature of the stabilities of the carbeniums and mechanisms of the hydride transfers between carbeniums and other hydride donors.

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.

Energy-consistent small-core pseudopotentials for 3d-transition metals adapted to quantum Monte Carlo calculations.

PubMed

Burkatzki, M; Filippi, Claudia; Dolg, M

2008-10-28

We extend our recently published set of energy-consistent scalar-relativistic Hartree-Fock pseudopotentials by the 3d-transition metal elements, scandium through zinc. The pseudopotentials do not exhibit a singularity at the nucleus and are therefore suitable for quantum Monte Carlo (QMC) calculations. The pseudopotentials and the accompanying basis sets (VnZ with n=T,Q) are given in standard Gaussian representation and their parameter sets are presented. Coupled cluster, configuration interaction, and QMC studies are carried out for the scandium and titanium atoms and their oxides, demonstrating the good performance of the pseudopotentials. Even though the choice of pseudopotential form is motivated by QMC, these pseudopotentials can also be employed in other quantum chemical approaches.

Laser ceramic materials for subpicosecond solid-state lasers using Nd3+-doped mixed scandium garnets.

PubMed

Okada, Hajime; Tanaka, Momoko; Kiriyama, Hiromitsu; Nakai, Yoshiki; Ochi, Yoshihiro; Sugiyama, Akira; Daido, Hiroyuki; Kimura, Toyoaki; Yanagitani, Takagimi; Yagi, Hideki; Meichin, Noriyuki

2010-09-15

We have successfully developed and demonstrated broadband emission Nd-doped mixed scandium garnets based on laser ceramic technology. The inhomogeneous broadening of Nd(3+) fluorescence lines results in a bandwidth above 5 nm that is significantly broader than that for Nd:YAG and enables subpicosecond mode-locked pulse durations. We have also found the emission cross section of 7.8 × 10(-20) cm(2) to be adequate for efficient energy extraction and thermal conductivity of 4.7 W/mK from these new Nd-doped laser ceramics. The new laser ceramics are good candidates for laser host material in a diode-pumped subpicosecond laser system with high efficiency and high repetition rate.

Synthesis of aluminum-based scandium-yttrium master alloys

NASA Astrophysics Data System (ADS)

Bazhin, V. Yu.; Kosov, Ya. I.; Lobacheva, O. L.; Dzhevaga, N. V.

2015-07-01

The preparation technology for an Al-2% Sc-0.5% Y master alloy using aluminum-manganese alloys has been developed and tested. The microstructure of the prepared master alloy is studied and the compositions of intermetallics is determined. The efficient technological parameters of the synthesis are determined. It is shown that varying the compositions of starting reagents and alloying additions and optimizing the process conditions (temperature, mixing, etc.) allow us to forecast the manufacturing and operating characteristics of aluminum-based master alloys. Joint additions of scandium and yttrium oxides to a charge favor a substantial decrease in the grain size of the formed intermetallics; this effect appears to the utmost in the case of microallying with yttrium up to 0.5 wt %.

SPECIATION OF ARSENIC COMPOUNDS IN DRINKING WATER BY CAPILLARY ELECTROPHORESIS WITH HYDRODYNAMICALLY MODIFIED ELECTROOSMOTIC FLOW DETECTED THROUGH HYDRIDE GENERATION INDUCTIVELY COUPLED PLASMA MASS..

EPA Science Inventory

Capillary electrophoresis (CE) was used to speciate four environmentally significant, toxic forms of arsenic: arsenite, arsenate, monomethylarsonic acid and dimethylarsinic acid. Hydride generation (HG) was used to convert the species into their respective hydrides. The hydride ...

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.

Hydrogen storage materials and method of making by dry homogenation

DOEpatents

Jensen, Craig M.; Zidan, Ragaiy A.

2002-01-01

Dry homogenized metal hydrides, in particular aluminum hydride compounds, as a material for reversible hydrogen storage is provided. The reversible hydrogen storage material comprises a dry homogenized material having transition metal catalytic sites on a metal aluminum hydride compound, or mixtures of metal aluminum hydride compounds. A method of making such reversible hydrogen storage materials by dry doping is also provided and comprises the steps of dry homogenizing metal hydrides by mechanical mixing, such as be crushing or ball milling a powder, of a metal aluminum hydride with a transition metal catalyst. In another aspect of the invention, a method of powering a vehicle apparatus with the reversible hydrogen storage material is provided.

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.

Gas-controlled dynamic vacuum insulation with gas gate

DOEpatents

Benson, David K.; Potter, Thomas F.

1994-06-07

Disclosed is a dynamic vacuum insulation comprising sidewalls enclosing an evacuated chamber and gas control means for releasing hydrogen gas into a chamber to increase gas molecule conduction of heat across the chamber and retrieving hydrogen gas from the chamber. The gas control means includes a metal hydride that absorbs and retains hydrogen gas at cooler temperatures and releases hydrogen gas at hotter temperatures; a hydride heating means for selectively heating the metal hydride to temperatures high enough to release hydrogen gas from the metal hydride; and gate means positioned between the metal hydride and the chamber for selectively allowing hydrogen to flow or not to flow between said metal hydride and said chamber.

Gas-controlled dynamic vacuum insulation with gas gate

DOEpatents

Benson, D.K.; Potter, T.F.

1994-06-07

Disclosed is a dynamic vacuum insulation comprising sidewalls enclosing an evacuated chamber and gas control means for releasing hydrogen gas into a chamber to increase gas molecule conduction of heat across the chamber and retrieving hydrogen gas from the chamber. The gas control means includes a metal hydride that absorbs and retains hydrogen gas at cooler temperatures and releases hydrogen gas at hotter temperatures; a hydride heating means for selectively heating the metal hydride to temperatures high enough to release hydrogen gas from the metal hydride; and gate means positioned between the metal hydride and the chamber for selectively allowing hydrogen to flow or not to flow between said metal hydride and said chamber. 25 figs.

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

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

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.

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.

SPECIATION OF ARSENIC COMPOUNDS IN DRINKING WATER BY CAPILLARY ELECTROPHORESIS WITH HYDRODYNAMICALLY MODIFIED ELECTROOSMOTIC FLOW DETECTED THROUGH HYDRIDE GENERATION INDUCTIVELY COUPLED PLASMA MASS...

EPA Science Inventory

Capillary electrophoresis (CE) was used to speciate four environmentally significant, toxic forms of arsenic: arsenite, arsenate, monomethylarsonic acid and dimethylarsinic acid. Hydride generation (HG) was used to convert the species into their respective hydrides. The hydride s...

Metal Hydrides for High-Temperature Power Generation

DOE PAGES

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

2015-08-10

Metal hydrides can be utilized for hydrogen storage and for thermal energy storage (TES) applications. By using TES with solar technologies, heat can be stored from sun energy to be used later which enables continuous power generation. We are developing a TES technology based on a dual-bed metal hydride system, which has a high-temperature (HT) metal hydride operating reversibly at 600-800°C to generate heat as well as a low-temperature (LT) hydride near room temperature that is used for hydrogen storage during sun hours until there is a need to produce electricity, such as during night time, a cloudy day, ormore » during peak hours. We proceeded from selecting a high-energy density, low-cost HT-hydride based on performance characterization on gram size samples, to scale-up to kilogram quantities and design, fabrication and testing of a 1.5kWh, 200kWh/m 3 bench-scale TES prototype based on a HT-bed of titanium hydride and a hydrogen gas storage instead of a LT-hydride. COMSOL Multiphysics was used to make performance predictions for cylindrical hydride beds with varying diameters and thermal conductivities. Based on experimental and modeling results, a bench-scale prototype was designed and fabricated and we successfully showed feasibility to meet or exceed all performance targets.« less

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.

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 correlating the finite element stress-state results with the spatial distribution of hydride microstructures observed within the optical micrographs for each sample. Experiments showed that the hydride reorientation was enhanced as the stress biaxiality increased. The threshold stress decreased from 150 MPa to 80 MPa when stress biaxiality ratio increased from uniaxial tension to near-equibiaxial tension. This behavior was also predicted by classical nucleation theory based on the Gibbs free energy of transformation being assisted by the far-field stress. An analysis of in situ X-ray diffraction data obtained during a thermo-mechanical cycle typical of vacuum drying showed a complex lattice-spacing behavior of the hydride phase during the dissolution and precipitation. The in-plane hydrides showed bilinear lattice expansion during heating with the intrinsic thermal expansion rate of the hydrides being observed only at elevated temperatures as they dissolve. For radial hydrides that precipitate during cooling under stress, the spacing of the close-packed {111} planes oriented normal to the maximum applied stress was permanently higher than the corresponding {111} plane spacing in the other directions. This behavior is believed to be a result of a complex stress state within the precipitating plate-like hydrides that induces a strain component within the hydrides normal to its "plate" face (i.e., the applied stress direction) that exceeds the lattice spacing strains in the other directions. During heat-up, the lattice spacing of these same "plate" planes actually contract due to the reversion of the stress state within the plate-like hydrides as they dissolve. The presence of radial hydrides and their connectivity with in-plane hydrides was shown to increase the ductile-to-brittle transition temperature during tensile testing. This behavior can be understood in terms of the role of radial hydrides in promoting the initiation of a long crack that subsequently propagates under fracture mechanics conditions. Finally, the d-spacing of irradiated Zircaloy-4 and M5 cladding tubes was measured at room temperature and compared to that of unirradiated samples.

Vanadium hydride deuterium-tritium generator

DOEpatents

Christensen, Leslie D.

1982-01-01

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

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.

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.

Proton-induced production and radiochemical isolation of 44Ti from scandium metal targets for 44Ti/44Sc generator development.

PubMed

Radchenko, Valery; Engle, Jonathan W; Medvedev, Dmitri G; Maassen, Joel M; Naranjo, Cleo M; Unc, George A; Meyer, Catherine A L; Mastren, Tara; Brugh, Mark; Mausner, Leonard; Cutler, Cathy S; Birnbaum, Eva R; John, Kevin D; Nortier, F Meiring; Fassbender, Michael E

2017-07-01

Scandium-44g (half-life 3.97h) shows promise for application in positron emission tomography (PET), due to favorable decay parameters. One of the sources of 44g Sc is the 44 Ti/ 44g Sc generator, which can conveniently provide this radioisotope on a daily basis at a diagnostic facility. Titanium-44 (half-life 60.0 a), in turn, can be obtained via proton irradiation of scandium metal targets. A substantial 44 Ti product batch, however, requires high beam currents, long irradiation times and an elaborate chemical procedure for 44 Ti isolation and purification. This study describes the production of a combined 175MBq (4.7mCi) batch yield of 44 Ti in week long proton irradiations at the Los Alamos Isotope Production Facility (LANL-IPF) and the Brookhaven Linac Isotope Producer (BNL-BLIP). A two-step ion exchange chromatography based chemical separation method is introduced: first, a coarse separation of 44 Ti via anion exchange sorption in concentrated HCl results in a 44 Tc/Sc separation factor of 10 2 -10 3 . A second, cation exchange based step in HCl media is then applied for 44 Ti fine purification from residual Sc mass. In summary, this method yields a 90-97% 44 Ti recovery with an overall Ti/Sc separation factor of ≥10 6 . Copyright © 2017 Elsevier Inc. All rights reserved.

Proton induced production and radiochemical isolation of 44Ti from scandium metal targets for 44Ti/ 44Sc generator development

DOE PAGES

Radchenko, Valery; Engle, Jonathan Ward; Medvedev, Dmitri G.; ...

2017-04-07

Scandium-44 g (half-life 3.97 h) shows promise for application in positron emission tomography (PET), due to favorable decay parameters. One of the sources of 44gSc is the 44Ti/ 44gSc generator, which can conveniently provide this radioisotope on a daily basis at a diagnostic facility. Titanium-44 (half-life 60.0 a), in turn, can be obtained via proton irradiation of scandium metal targets. A substantial 44Ti product batch, however, requires high beam currents, long irradiation times and an elaborate chemical procedure for 44Ti isolation and purification. This study describes the production of a combined 175 MBq (4.7 mCi) batch yield of 44Ti inmore » week long proton irradiations at the Los Alamos Isotope Production Facility (LANL-IPF) and the Brookhaven Linac Isotope Producer (BNL-BLIP). A two-step ion exchange chromatography based chemical separation method is introduced: first, a coarse separation of 44Ti via anion exchange sorption in concentrated HCl results in a 44Tc/Sc separation factor of 10 2–10 3. A second, cation exchange based step in HCl media is then applied for 44Ti fine purification from residual Sc mass. In conclusion, this method yields a 90–97% 44Ti recovery with an overall Ti/Sc separation factor of ≥10 6.« less

Major- and trace-element concentrations in soils from two continental-scale transects of the United States and Canada

USGS Publications Warehouse

Smith, David B.; Cannon, William F.; Woodruff, Laurel G.; Garrett, Robert G.; Klassen, Rodney; Kilburn, James E.; Horton, John D.; King, Harley D.; Goldhaber, Martin B.; Morrison, Jean M.

2005-01-01

This report contains major- and trace-element concentration data for soil samples collected from 265 sites along two continental-scale transects in North America. One of the transects extends from northern Manitoba to the United States-Mexico border near El Paso, Tex. and consists of 105 sites. The other transect approximately follows the 38th parallel from the Pacific coast of the United States near San Francisco, Calif., to the Atlantic coast along the Maryland shore and consists of 160 sites. Sampling sites were defined by first dividing each transect into approximately 40-km segments. For each segment, a 1-km-wide latitudinal strip was randomly selected; within each strip, a potential sample site was selected from the most representative landscape within the most common soil type. At one in four sites, duplicate samples were collected 10 meters apart to estimate local spatial variability. At each site, up to four separate soil samples were collected as follows: (1) material from 0-5 cm depth; (2) O horizon, if present; (3) a composite of the A horizon; and (4) C horizon. Each sample collected was analyzed for total major- and trace-element composition by the following methods: (1) inductively coupled plasmamass spectrometry (ICP-MS) and inductively coupled plasma-atomic emission spectrometry (ICPAES) for aluminum, antimony, arsenic, barium, beryllium, bismuth, cadmium, calcium, cerium, cesium, chromium, cobalt, copper, gallium, indium, iron, lanthanum, lead, lithium, magnesium, manganese, molybdenum, nickel, niobium, phosphorus, potassium, rubidium, scandium, silver, sodium, strontium, sulfur, tellurium, thallium, thorium, tin, titanium, tungsten, uranium, vanadium, yttrium, and zinc; (2) cold vapor- atomic absorption spectrometry for mercury; (3) hydride generation-atomic absorption spectrometry for antimony and selenium; (4) coulometric titration for carbonate carbon; and (5) combustion for total carbon and total sulfur.

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.

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.

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##

Vanadium hydride deuterium-tritium generator

DOEpatents

Christensen, L.D.

1980-03-13

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

Phase stable rare earth garnets

DOEpatents

Kuntz, Joshua D.; Cherepy, Nerine J.; Roberts, Jeffery J.; Payne, Stephen A.

2013-06-11

A transparent ceramic according to one embodiment includes a rare earth garnet comprising A.sub.hB.sub.iC.sub.jO.sub.12, where h is 3.+-.10%, i is 2.+-.10%, and j is 3.+-.10%. A includes a rare earth element or a mixture of rare earth elements, B includes at least one of aluminum, gallium and scandium, and C includes at least one of aluminum, gallium and scandium, where A is at a dodecahedral site of the garnet, B is at an octahedral site of the garnet, and C is at a tetrahedral site of the garnet. In one embodiment, the rare earth garment has scintillation properties. A radiation detector in one embodiment includes a transparent ceramic as described above and a photo detector optically coupled to the rare earth garnet.

Intracavity frequency doubling of a continuous-wave, diode-laser-pumped neodymium lanthanum scandium borate laser.

PubMed

Meyn, J P; Huber, G

1994-09-15

Neodymium-doped lanthanum scandium borate [Nd:LaSc(3)(BO(3))(4)] is a new material for efficient and compact diode-pumped solid-state lasers. A simple plane-plane 3-mm-long resonator is formed by a coated Nd(10%):LaSc(3)(BO(3))(4) crystal and a coated potassium titanyl phosphate (KTP) crystal. The second-harmonic output power at 531 nm is 522 mW at 2.05-W incident pump power of the diode laser. The corresponding optical efficiency is 25%, and the conversion efficiency from the fundamental to the second harmonic is 55%. The wellknown chaotic power fluctuations of intracavity frequency-doubled lasers (green problem) are avoided by use of a short KTP crystal, between 0.5 and 2 mm in length.

Aqueous Hydricity of Late Metal Catalysts as a Continuum Tuned by Ligands and the Medium.

PubMed

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

2016-02-24

Aqueous hydride transfer is a fundamental step in emerging alternative energy transformations such as H2 evolution and CO2 reduction. "Hydricity," the hydride donor ability of a species, is a key metric for understanding transition metal hydride reactivity, but comprehensive studies of aqueous hydricity are scarce. An extensive and self-consistent aqueous hydricity scale is constructed for a family of Ru and Ir hydrides that are key intermediates in aqueous catalysis. A reference hydricity is determined using redox potentiometry and spectrophotometric titration for a particularly water-soluble species. Then, relative hydricity values for a range of species are measured using hydride transfer equilibria, taking advantage of expedient new synthetic procedures for Ru and Ir hydrides. This large collection of hydricity values provides the most comprehensive picture so far of how ligands impact hydricity in water. Strikingly, we also find that hydricity can be viewed as a continuum in water: the free energy of hydride transfer changes with pH, buffer composition, and salts present in solution.

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.

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.

Process for recovering evolved hydrogen enriched with at least one heavy hydrogen isotope

DOEpatents

Tanaka, John; Reilly, Jr., James J.

1978-01-01

This invention relates to a separation means and method for enriching a hydrogen atmosphere with at least one heavy hydrogen isotope by using a solid titaniun alloy hydride. To this end, the titanium alloy hydride containing at least one metal selected from the group consisting of vanadium, chromium, manganese, molybdenum, iron, cobalt and nickel is contacted with a circulating gaseous flow of hydrogen containing at least one heavy hydrogen isotope at a temperature in the range of -20.degree. to +40.degree. C and at a pressure above the dissociation pressure of the hydrided alloy selectively to concentrate at least one of the isotopes of hydrogen in the hydrided metal alloy. The contacting is continued until equilibrium is reached, and then the gaseous flow is isolated while the temperature and pressure of the enriched hydride remain undisturbed selectively to isolate the hydride. Thereafter, the enriched hydrogen is selectively recovered in accordance with the separation factor (S.F.) of the alloy hydride employed.

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.

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.

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.

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.

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}.

Polyhydrido Copper Clusters: Synthetic Advances, Structural Diversity, and Nanocluster-to-Nanoparticle Conversion.

PubMed

Dhayal, Rajendra S; van Zyl, Werner E; Liu, C W

2016-01-19

Metal hydride clusters have historically been studied to unravel their aesthetically pleasing molecular structures and interesting properties, especially toward hydrogen related applications. Central to this work is the hydride ligand, H¯, the smallest closed-shell spherical anion known. Two new developments in polyhydrido nanocluster chemistry include the determination of heretofore unknown hydride coordination modes and novel structural constructs, and conversion from the molecular entities to rhombus-shaped copper nanoparticles (CuNPs). These advances, together with hydrogen evolution and catalysis, have provided both experimentalists and theorists with a rich scientific directive to further explore. The isolation of hexameric [{(Ph3P)CuH}6] (Stryker reagent) could be regarded as the springboard for the recent emergence of polyhydrido copper cluster chemistry due to its utilization in a variety of organic chemical transformations. The stability of clusters of various nuclearity was improved through phosphine, pyridine, and carbene type ligands. Our focus lies with the isolation of novel copper (poly)hydride clusters using mostly the phosphor-1,1-dithiolato type ligands. We found such chalcogen-stabilized clusters to be exceptionally air and moisture stable over a wide range of nuclearities (Cu7 to Cu32). In this Account, we (i) report on state-of-the-art copper hydride cluster chemistry, especially with regards to the diverse and novel structural types generally, and newly discovered hydride coordination modes in particular, (ii) demonstrate the indispensable power of neutron diffraction for the unambiguous assignment and location of hydride ligand(s) within a cluster, and (iii) prove unique transformations that can occur not only between well characterized high nuclearity clusters, but also how such clusters can transform to uniquely shaped nanoparticles of several nanometers in diameter through copper hydride reduction. The increase in the number of low- to high-nuclearity hydride clusters allows for different means by which they can be classified. We chose a classification based on the coordination mode of hydride ligand within the cluster. This includes copper clusters associated with bridging (μ2-H) and capping (μ3-H) hydride modes, followed by an interstitial (μ4-H) hydride mode that was introduced for the first time into octa- and hepta-nuclear copper clusters stabilized by dichalcogen-type ligands. This breakthrough provided a means to explore higher nuclearity polyhydrido nanoclusters, which contain both capping (μ3-H) and interstitial (μ(4-6)-H) hydrides. The presence of bidentate ligands having mixed S/P dative sites led to air- and moisture-stable copper hydride nanoclusters. The formation of rhombus-shaped nanoparticles (CuNPs) from copper polyhydrides in the presence of excess borohydrides suggests the presence of metal hydrides as intermediates during the formation of nanoparticles.

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 alanates. Complex hydrides exhibited very high compressibility suggesting possibility to destabilize them with pressure. With high capacity and favorable thermodynamics, complex hydrides are suitable for reversible storage. Further studies are required to overcome the kinetic barriers in complex hydrides by catalytic addition. A comparative study of the hydride properties with that of the constituting metal, and their inter relationships were carried out with many interesting features.

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.

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 contributing parameters. These contributing factors need to be recognized and a means to control them or separate their contributions will be required to obtain the desired information.« less

Method for controlled hydrogen charging of metals

DOEpatents

Cheng, Bo-Ching; Adamson, Ronald B.

1984-05-29

A method for controlling hydrogen charging of hydride forming metals through a window of a superimposed layer of a non-hydriding metal overlying the portion of the hydride forming metals to be charged.

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.

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

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 chamber (1)–Cu(1.83 wt. %)Be as a standard, the peak intensity from chamber (4)—stainless-steel (air-fired) was 7.1× higher, indicating that the surface of stainless-steel had a larger concentration of reactive oxygen and/or water than hydrogen. The (D{sub 2}O{sup +}) peak intensity from chamber (3)—Cu (interior Al coating) was 1.55× larger and chamber (2)—alumina(99.8%) was 1.33× higher than Cu(1.83 wt. %)Be. Thus copper–(1.83 wt. %)beryllium was the best hydriding chamber material studied followed closely by the alumina (99.8 wt. %) chamber. Gas take-up by Er occluder targets processed in Cu(1.83 wt. %)Be hydriding chambers (i.e., gas/metal atomic ratios) correlate with the dynamic RGA data.« less

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.

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

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.

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.

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 tests of hydrided Zircaloy-4 cladding, which served as a guideline to prepare in-cell hydride reorientation samples with high burnup HBR fuel segments. This report also provides the Phase II CIRFT test data for the hydride reorientation irradiated samples. The variations in fatigue life are provided in terms of moment, equivalent stress, curvature, and equivalent strain for the tested SNFs. The CIRFT results appear to indicate that hydride reoriented treatment (HRT) have a negative effect on fatigue life, in addition to hydride reorientation effect. For HR4 specimen that had no pressurization procedure applied, the thermal annealing treatment alone showed a negative impact on the fatigue life compared to the HBR rod.« less

Electron linear accelerator production and purification of scandium-47 from titanium dioxide targets.

PubMed

Rotsch, David A; Brown, M Alex; Nolen, Jerry A; Brossard, Thomas; Henning, Walter F; Chemerisov, Sergey D; Gromov, Roman G; Greene, John

2018-01-01

The photonuclear production of no-carrier-added (NCA) 47 Sc from solid Nat TiO 2 and the subsequent chemical processing and purification have been developed. Scandium-47 was produced by the 48 Ti(γ,p) 47 Sc reaction with Bremsstrahlung photons produced from the braking of electrons in a high-Z (W or Ta) convertor. Production yields were simulated with the PHITS code (Particle and Heavy Ion Transport-code System) and compared to experimental results. Irradiated TiO 2 targets were dissolved in fuming H 2 SO 4 in the presence of Na 2 SO 4 and 47 Sc was purified using the commercially available Eichrom DGA resin. Typical 47 Sc recovery yields were >90% with excellent specific activity for small batches (<185 MBq batches). Copyright © 2017 Elsevier Ltd. All rights reserved.

Electron linear accelerator production and purification of scandium-47 from titanium dioxide targets

DOE PAGES

Rotsch, David A.; Brown, M. Alex; Nolen, Jerry A.; ...

2017-11-06

Here, the photonuclear production of no-carrier-added (NCA) 47Sc from solid NatTiO 2 and the subsequent chemical processing and purification have been developed. Scandium-47 was produced by the 48Ti(γ,p) 47Sc reaction with Bremsstrahlung photons produced from the braking of electrons in a high-Z (W or Ta) convertor. Production yields were simulated with the PHITS code (Particle and Heavy Ion Transport-code System) and compared to experimental results. Irradiated TiO 2 targets were dissolved in fuming H 2SO 4 in the presence of Na 2SO 4 and 47Sc was purified using the commercially available Eichrom DGA resin. Typical 47Sc recovery yields were >90%more » with excellent specific activity for small batches (<185 MBq batches).« less

Electron linear accelerator production and purification of scandium-47 from titanium dioxide targets

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

Rotsch, David A.; Brown, M. Alex; Nolen, Jerry A.

Here, the photonuclear production of no-carrier-added (NCA) 47Sc from solid NatTiO 2 and the subsequent chemical processing and purification have been developed. Scandium-47 was produced by the 48Ti(γ,p) 47Sc reaction with Bremsstrahlung photons produced from the braking of electrons in a high-Z (W or Ta) convertor. Production yields were simulated with the PHITS code (Particle and Heavy Ion Transport-code System) and compared to experimental results. Irradiated TiO 2 targets were dissolved in fuming H 2SO 4 in the presence of Na 2SO 4 and 47Sc was purified using the commercially available Eichrom DGA resin. Typical 47Sc recovery yields were >90%more » with excellent specific activity for small batches (<185 MBq batches).« less

A study on the reaction of Zircaloy-4 tube with hydrogen/steam mixture

NASA Astrophysics Data System (ADS)

Lee, Ji-Min; Kook, Dong-Hak; Cho, Il-Je; Kim, Yong-Soo

2017-08-01

In order to fundamentally understand the secondary hydriding mechanism of zirconium alloy cladding, the reaction of commercial Zircaloy-4 tubes with hydrogen and steam mixture was studied using a thermo-gravimetric analyser with two variables, H2/H2O ratio and temperature. Phenomenological analysis revealed that in the steam starvation condition, i.e., when the H2/H2O ratio is greater than 104, hydriding is the dominant reaction and the weight gain increases linearly after a short incubation time. On the other hand, when the gas ratio is 5 × 102 or 103, both hydriding and oxidation reactions take place simultaneously, leading to three distinct regimes: primary hydriding, enhanced oxidation, and massive hydriding. Microstructural changes of oxide demonstrate that when the weight gain exceeds a certain critical value, massive hydriding takes place due to the significant localized crack development within the oxide, which possibly simulates the secondary hydriding failure in a defective fuel operation. This study reveals that the steam starvation condition above the critical H2/H2O ratio is only a necessary condition for the secondary hydriding failure and, as a sufficient condition, oxide needs to grow sufficiently to reach the critical thickness that produces substantial crack development. In other words, in a real defective fuel operation incident, the secondary failure is initiated only when both steam starvation and oxide degradation conditions are simultaneously met. Therefore, it is concluded that the indispensable time for the critical oxide growth primarily determines the triggering time of massive hydriding failure.

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.

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.

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

Hydrolysis reactor for hydrogen production

DOEpatents

Davis, Thomas A.; Matthews, Michael A.

2012-12-04

In accordance with certain embodiments of the present disclosure, a method for hydrolysis of a chemical hydride is provided. The method includes adding a chemical hydride to a reaction chamber and exposing the chemical hydride in the reaction chamber to a temperature of at least about 100.degree. C. in the presence of water and in the absence of an acid or a heterogeneous catalyst, wherein the chemical hydride undergoes hydrolysis to form hydrogen gas and a byproduct material.

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.

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 have demonstrated the technical viability of the process and have provided data for the cost analyses that have been performed. We also concluded that a carbothermic process could also produce magnesium at acceptable costs. The use of slurry as a medium to carry chemical hydrides has been shown during this project to offer significant advantages for storing, delivering, and distributing hydrogen: • Magnesium hydride slurry is stable for months and pumpable. • The oils of the slurry minimize the contact of oxygen and moisture in the air with the metal hydride in the slurry. Thus reactive chemicals, such as lithium hydride, can be handled safely in the air when encased in the oils of the slurry. • Though magnesium hydride offers an additional safety feature of not reacting readily with water at room temperatures, it does react readily with water at temperatures above the boiling point of water. Thus when hydrogen is needed, the slurry and water are heated until the reaction begins, then the reaction energy provides heat for more slurry and water to be heated. • The reaction system can be relatively small and light and the slurry can be stored in conventional liquid fuel tanks. When transported and stored, the conventional liquid fuel infrastructure can be used. • The particular metal hydride of interest in this project, magnesium hydride, forms benign byproducts, magnesium hydroxide (“Milk of Magnesia”) and magnesium oxide. • We have estimated that a magnesium hydride slurry system (including the mixer device and tanks) could meet the DOE 2010 energy density goals. During the investigation of hydriding techniques, we learned that magnesium hydride in a slurry can also be cycled in a rechargeable fashion. Thus, magnesium hydride slurry can act either as a chemical hydride storage medium or as a rechargeable hydride storage system. Hydrogen can be stored and delivered and then stored again thus significantly reducing the cost of storing and delivering hydrogen. Further evaluation and development of this concept will be performed as follow-on work under another project. However, since the cost of reducing magnesium from magnesium oxide makes up 85% of the cost of the slurry, if hydrogen can be stored many times in the slurry, then the cost of storing hydrogen can be spread over many units of hydrogen and can be significantly reduced from the costs of a chemical hydride system. This may be the most important finding of this project. If the slurry is used to carry a rechargeable hydride, the slurry can be stored in a conventional liquid fuel tank and delivered to a release system as hydrogen is needed. The release system will contain only the hydride needed to produce the hydrogen desired. This is in contrast to conventional designs proposed for other rechargeable hydride systems that store all the hydride in a large and heavy pressure and heat transfer vessel.« less

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.

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 combined theoretical and experimental approach may be valuable for characterization of analogous redox states in the [NiFe] hydrogenases.

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

Investigation of the reaction of 5Al-2.5Sn titanium with hydrogen at subzero temperature

NASA Technical Reports Server (NTRS)

Williams, D. N.; Wood, R. A.

1972-01-01

An investigation of the effect of temperature on the surface hydriding reaction of 5Al-2.5Sn titanium exposed to hydrogen at 250 psig was made. The temperature range studied extended from 160 F to -160 F. Reaction conditions were controlled so as to expose a vacuum-cleaned, oxide-free alloy surface to an ultrapure hydrogen atmosphere. Reaction times up to 1458 hours were studied. The hydriding reaction was extremely sensitive to experimental variables and the reproducibility of reaction behavior was poor. However, it was demonstrated that the reaction proceeded quite rapidly at 160 F; as much as 1 mil surface hydriding being observed after exposure for 162 hours. The amount of hydriding appeared to decrease with decreasing temperature at 75 F, -36 F, and -76 F. No surface hydriding was detected either by vacuum fusion analysis or by metallographic examination after exposure for 1458 hours at -110 F or -160 F. Tensile properties were unaffected by surface hydriding of the severity developed in this program (up to 1 mil thick) as determined by slow strain rate testing of hydrided sheet tensile samples.

Apparatus for chemical synthesis

DOEpatents

Kong, Peter C [Idaho Falls, ID; Herring, J Stephen [Idaho Falls, ID; Grandy, Jon D [Idaho Falls, ID

2011-05-10

A method and apparatus for forming a chemical hydride is described and which includes a pseudo-plasma-electrolysis reactor which is operable to receive a solution capable of forming a chemical hydride and which further includes a cathode and a movable anode, and wherein the anode is moved into and out of fluidic, ohmic electrical contact with the solution capable of forming a chemical hydride and which further, when energized produces an oxygen plasma which facilitates the formation of a chemical hydride in the solution.

Method and apparatus for chemical synthesis

DOEpatents

Kong; Peter C. , Herring; J. Stephen , Grandy; Jon D.

2007-12-04

A method and apparatus for forming a chemical hydride is described and which includes a pseudo-plasma-electrolysis reactor which is operable to receive a solution capable of forming a chemical hydride and which further includes a cathode and a movable anode, and wherein the anode is moved into and out of fluidic, ohmic electrical contact with the solution capable of forming a chemical hydride and which further, when energized produces an oxygen plasma which facilitates the formation of a chemical hydride in the solution.

The Crystal Structure of Thorium and Zirconium Dihydrides by X-ray and Neutron Diffraction

DOE R&D Accomplishments Database

Rundle, R.E.; Shull, C.G.; Wollan, E.O.

1951-04-20

Thorium forms a tetragonal lower hydride of composition ThH{sub 2}. The hydrides ThH{sub 2}, ThD{sub 2}, and ZrD{sub 2} have been studied by neutron diffraction in order that hydrogen positions could be determined. The hydrides are isomorphous, and have a deformed fluorite structure. Metal-hydrogen distances in thorium hydride are unusually large, as in UH{sub 3}. Thorium and zirconium scattering amplitudes and a revised scattering amplitude for deuterium are reported.

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.

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.

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.

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.

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.

Thermal desorption of hydrogen from Mg2Ni hydrogen storage materials.

PubMed

Hur, Tae Hong; Han, Jeong Seb; Kim, Jin Ho; Kim, Byung Kwan

2011-07-01

In order to investigate the influence of HCS on the hydrogen occupation site of Mg2Ni alloy, the thermal desorption technique has been applied to Mg2Ni hydride made by hydriding combustion synthesis (HCS). Mg2Ni was made under low temperature in a short time by the HCS compared to conventional melting process. At various initial hydride wt% from 0.91 to 3.52, the sample was heated to 623 K at a rate of 1.0 K/min. The starting temperature of the evolution of hydrogen goes higher as the initial hydride wt% increases. Only one peak is shown in the case of the small initial hydride wt%. But two peaks appeared with increasing initial hydride wt%. The activation energies obtained by the first and second peaks are 113.0 and 99.5 kJ/mol respectively. The two site occupation model by Darriet et al. was proved. The influence of HCS on the hydrogen occupation site of Mg2Ni alloy is nonexistent.

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

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.

Scandium Terminal Imido Chemistry.

PubMed

Lu, Erli; Chu, Jiaxiang; Chen, Yaofeng

2018-02-20

Research into transition metal complexes bearing multiply bonded main-group ligands has developed into a thriving and fruitful field over the past half century. These complexes, featuring terminal M═E/M≡E (M = transition metal; E = main-group element) multiple bonds, exhibit unique structural properties as well as rich reactivity, which render them attractive targets for inorganic/organometallic chemists as well as indispensable tools for organic/catalytic chemists. This fact has been highlighted by their widespread applications in organic synthesis, for example, as olefin metathesis catalysts. In the ongoing renaissance of transition metal-ligand multiple-bonding chemistry, there have been reports of M═E/M≡E interactions for the majority of the metallic elements of the periodic table, even some actinide metals. In stark contrast, the largest subgroup of the periodic table, rare-earth metals (Ln = Sc, Y, and lanthanides), have been excluded from this upsurge. Indeed, the synthesis of terminal Ln═E/Ln≡E multiple-bonding species lagged behind that of the transition metal and actinide congeners for decades. Although these species had been pursued since the discovery of a rare-earth metal bridging imide in 1991, such a terminal (nonpincer/bridging hapticities) Ln═E/Ln≡E bond species was not obtained until 2010. The scarcity is mainly attributed to the energy mismatch between the frontier orbitals of the metal and the ligand atoms. This renders the putative terminal Ln═E/Ln≡E bonds extremely reactive, thus resulting in the formation of aggregates and/or reaction with the ligand/environment, quenching the multiple-bond character. In 2010, the stalemate was broken by the isolation and structural characterization of the first rare-earth metal terminal imide-a scandium terminal imide-by our group. The double-bond character of the Sc═N bond was unequivocally confirmed by single-crystal X-ray diffraction. Theoretical investigations revealed the presence of two p-d π bonds between the scandium ion and the nitrogen atom of the imido ligand and showed that the dianionic [NR] 2- imido ligand acts as a 2σ,4π electron donor. Subsequent studies of the scandium terminal imides revealed highly versatile and intriguing reactivity of the Sc═N bond. This included cycloaddition toward various unsaturated bonds, C-H/Si-H/B-H bond activations and catalytic hydrosilylation, dehydrofluorination of fluoro-substituted benzenes/alkanes, CO 2 and H 2 activations, activation of elemental selenium, coordination with other transition metal halides, etc. Since our initial success in 2010, and with contributions from us and across the community, this young, vibrant research field has rapidly flourished into one of the most active frontiers of rare-earth metal chemistry. The prospect of extending Ln═N chemistry to other rare-earth metals and/or different metal oxidation states, as well as exploiting their stoichiometric and catalytic reactivities, continues to attract research effort. Herein we present an account of our investigations into scandium terminal imido chemistry as a timely summary, in the hope that our studies will be of interest to this readership.

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.

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.

Formal Synthesis of (±)-Roseophilin

PubMed Central

Bitar, Abdallah Y.; Frontier, Alison J.

2009-01-01

A formal synthesis of (±)-roseophilin is described. Scandium(III)-catalyzed Nazarov cyclization of 2,5-disubstituted N-tosylpyrrole 19 gives a 5,5’-fused ketopyrrole, and ansa-bridge formation via π-allyl palladium macrocyclization gives 21. PMID:19053717

Investigation of concentration-dependence of thermodynamic properties of lanthanum, yttrium, scandium and terbium in eutectic LiCl-KCl molten salt

NASA Astrophysics Data System (ADS)

Wang, Yafei; Zhou, Wentao; Zhang, Jinsuo

2016-09-01

Thermodynamic properties of rare earth metals in LiCl-KCl molten salt electrolyte are crucial to the development of electrochemical separation for the treatment of used nuclear fuels. In the present study, activity coefficient, apparent potential, and diffusion coefficient of lanthanum, yttrium, scandium, and terbium in the molten salt (58 at% LiCl and 42 at% KCl) were calculated by the method of molecular dynamics simulation up to a concentration around 3 at% at temperatures of 723 K and 773 K. It was found that the activity coefficient and the apparent potential increase with the species concentration while diffusion coefficient shows a trend of increase followed by decrease. The calculated results were validated by available measurement data of dilution cases. This research extends the range of data to a wide component and would provide further insight to the pyroprocessing design and safeguards.

Improvement in the Shape Memory Response of Ti50.5Ni24.5Pd25 High-Temperature Shape Memory Alloy with Scandium Microalloying

NASA Technical Reports Server (NTRS)

Atli, K. C.; Karaman, I; Noebe, R. D.; Garg, A.; Chumlyakov, Y. I.; Kireeva, I. V.

2010-01-01

A Ti(50.5)Ni(24.5)Pd25 high-temperature shape memory alloy (HTSMA) is microalloyed with 0.5 at. pct scandium (Sc) to enhance its shape-memory characteristics, in particular, dimensional stability under repeated thermomechanical cycles. For both Ti(50.5)Ni(24.5)Pd25 and the Sc-alloyed material, differential scanning calorimetry is conducted for multiple cycles to characterize cyclic stability of the transformation temperatures. The microstructure is evaluated using electron microscopy, X-ray diffractometry, and wavelength dispersive spectroscopy. Isobaric thermal cycling experiments are used to determine transformation temperatures, dimensional stability, and work output as a function of stress. The Sc-doped alloy displays more stable shape memory response with smaller irrecoverable strain and narrower thermal hysteresis than the baseline ternary alloy. This improvement in performance is attributed to the solid solution hardening effect of Sc.

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

Radchenko, Valery; Meyer, Catherine Anne Louise; Engle, Jonathan Ward

Scandium-44 g (half-life 3.97 h) shows promise for positron emission tomography (PET) imaging of longer biological processes than that of the current gold standard, 18F, due to its favorable decay parameters. One source of 44gSc is the long-lived parent nuclide 44Ti (half-life 60.0 a). A 44Ti/ 44gSc generator would have the ability to provide radionuclidically pure 44gSc on a daily basis. The production of 44Ti via the 45Sc(p,2n) reaction requires high proton beam currents and long irradiation times. Recovery and purification of no-carrier added (nca) 44Ti from scandium metal targets involves complex separation chemistry. In this study, separation systems basedmore » on solid phase extraction chromatography were investigated, including branched diglycolamide (BDGA) resin and hydroxamate based ZR resin. Lastly, results indicate that ZR resin in HCl media represents an effective 44Ti/ 44gSc separation system.« less

Investigation of ionic transport in sodium scandium phosphate (NSP) and related compounds

NASA Astrophysics Data System (ADS)

Bhat, Kaustubh; Blügel, Stefan; Lustfeld, Hans

Sodium ionic conductors offer significant advantages for application in large scale energy storage systems. In this study, we investigate the different pathways available for sodium ion conduction in NSP and calculate energy barriers for ionic transport using Density Functional Theory (DFT) and the Nudged Elastic Band Method. We identify the structural parameters that reduce the energy barrier, by calculating the influence of positive and negative external pressure on the energy barrier. Lattice strain can be introduced by cation or anion substitution within the NASICON structure. We substitute the scandium atom with other trivalent atoms such as aluminium and yttrium, and calculate the resulting energy barriers. Sodium thiophosphate (Na3PS4) has previously shown about two orders of magnitude higher ionic conductivity than sodium phosphate (Na3PO4). We investigate the effect of substituting oxygen with sulphur in NSP. We acknowledge discussions with our experimental colleagues F. Tietz and M. Guin toward this work

Reducing the stochasticity of crystal nucleation to enable subnanosecond memory writing

NASA Astrophysics Data System (ADS)

Rao, Feng; Ding, Keyuan; Zhou, Yuxing; Zheng, Yonghui; Xia, Mengjiao; Lv, Shilong; Song, Zhitang; Feng, Songlin; Ronneberger, Ider; Mazzarello, Riccardo; Zhang, Wei; Ma, Evan

2017-12-01

Operation speed is a key challenge in phase-change random-access memory (PCRAM) technology, especially for achieving subnanosecond high-speed cache memory. Commercialized PCRAM products are limited by the tens of nanoseconds writing speed, originating from the stochastic crystal nucleation during the crystallization of amorphous germanium antimony telluride (Ge2Sb2Te5). Here, we demonstrate an alloying strategy to speed up the crystallization kinetics. The scandium antimony telluride (Sc0.2Sb2Te3) compound that we designed allows a writing speed of only 700 picoseconds without preprogramming in a large conventional PCRAM device. This ultrafast crystallization stems from the reduced stochasticity of nucleation through geometrically matched and robust scandium telluride (ScTe) chemical bonds that stabilize crystal precursors in the amorphous state. Controlling nucleation through alloy design paves the way for the development of cache-type PCRAM technology to boost the working efficiency of computing systems.

The Current Status of Hydrogen Storage Alloy Development for Electrochemical Applications.

PubMed

Young, Kwo-Hsiung; Nei, Jean

2013-10-17

In this review article, the fundamentals of electrochemical reactions involving metal hydrides are explained, followed by a report of recent progress in hydrogen storage alloys for electrochemical applications. The status of various alloy systems, including AB₅, AB₂, A₂B₇-type, Ti-Ni-based, Mg-Ni-based, BCC, and Zr-Ni-based metal hydride alloys, for their most important electrochemical application, the nickel metal hydride battery, is summarized. Other electrochemical applications, such as Ni-hydrogen, fuel cell, Li-ion battery, air-metal hydride, and hybrid battery systems, also have been mentioned.

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.

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.

Method for converting uranium oxides to uranium metal

DOEpatents

Duerksen, Walter K.

1988-01-01

A process is described for converting scrap and waste uranium oxide to uranium metal. The uranium oxide is sequentially reduced with a suitable reducing agent to a mixture of uranium metal and oxide products. The uranium metal is then converted to uranium hydride and the uranium hydride-containing mixture is then cooled to a temperature less than -100.degree. C. in an inert liquid which renders the uranium hydride ferromagnetic. The uranium hydride is then magnetically separated from the cooled mixture. The separated uranium hydride is readily converted to uranium metal by heating in an inert atmosphere. This process is environmentally acceptable and eliminates the use of hydrogen fluoride as well as the explosive conditions encountered in the previously employed bomb-reduction processes utilized for converting uranium oxides to uranium metal.

System for exchange of hydrogen between liquid and solid phases

DOEpatents

Reilly, James J.; Grohse, Edward W.; Johnson, John R.; Winsche, deceased, Warren E.

1988-01-01

The reversible reaction M+x/2 H.sub.2 .rarw..fwdarw.MH.sub.x, wherein M is a reversible 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 an inert liquid, thereby reducing contamination, providing better temperature control, providing in situ mobility of the reactants, and increasing flexibility in process design. Thus, a slurry of particles of a metal hydride former with an inert solvent is subjected to a temperature and pressure controlled atmosphere containing H.sub.2, to store hydrogen and to release 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 actual H.sub.2 pressure 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 particles. When the actual 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.

System for exchange of hydrogen between liquid and solid phases

DOEpatents

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

1985-02-22

The reversible reaction M + x/2 H/sub 2/ reversible MH/sub x/, wherein M is a reversible 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 an inert liquid, thereby reducing contamination, providing better temperature control, providing in situ mobility of the reactants, and increasing flexibility in process design. Thus, a slurry of particles of a metal hydride former with an inert solvent is subjected to a temperature and pressure controlled atmosphere containing H/sub 2/, to store hydrogen and to release 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 actual H/sub 2/ pressure 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 actual 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.

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-of-concept prototypes are built and tested, demonstrating the potential of the system as HVAC for transportation vehicles. The performance of the concept-demonstration-unit show both high heating/cooling power and high energy densities. An extended cycling test shows degradation on the performance of the system. To solve this problem, a metal hydride hydrogen compressor is proposed for aiding the recharge process of the system.

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 address these drawbacks. The development of high-capacity hydride anodes should be inspired by the emergent nano-research prospects which share the knowledge of both hydrogen-storage and lithium-anode communities. PMID:26425434

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 were dried in air at 40 C. The granules were heated to 230 C for 30 minutes in argon to remove the remaining water and organic materials. The resulting product was spherical composite granules (100 to 2000 micron diameter) with a porous silica matrix containing small agglomerates of metal hydride particles. Open porosity in the silica matrix allows hydrogen to permeate rapidly through the matrix but the pores are small enough to contain the metal hydride particles. Additional porosity around the metal hydride particles, induced using abietic acid as a pore former, allows the particles to freely expand and contract without fracturing the brittle sol-gel matrix. It was demonstrated that the granules readily absorb and desorb hydrogen while remaining integral and dimensionally stable. Microcracking was observed after the granules were cycled in hydrogen five times. The strength of the granules was improved by coating them with a thin layer of a micro-porous polymer sol-gel that would allow hydrogen to freely pass through the coating but would filter out metal hydride poisons such as water and carbon monoxide. It was demonstrated that if a thin sol-gel coating was applied after the granules were cycled, the coating not only improved the strength of the granules but the coated granules retained their strength after additional hydrogen cycling tests. This additional strength is needed to extend the lifetime of the granules and to survive the compressive load in a large column of granules. Additional hydrogen adsorption tests are planned to evaluate the performance of coated granules after one hundred cycles. Tests will also be performed to determine the effects of metal hydride poisons on the granules. The results of these tests will be documented in a separate report. The process that was developed to form these granules could be scaled to a production process. The process to form granules from a mixture of metal hydride particles and pore former such as abietic acid can be scaled up using commercial granulators. The current laboratory-scale external gelation column produces approximately one gram of granules per hour. To increase the production output from a single column, multiple feed injection systems in a larger diameter column could be used.« less

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

PubMed

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

2016-09-06

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

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.

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

NASA Astrophysics Data System (ADS)

Patki, Gauri Dilip

Hydrogen is a promising energy carrier, for use in fuel cells, engines, and turbines for transportation or mobile applications. Hydrogen is desirable as an energy carrier, because its oxidation by air releases substantial energy (thermally or electrochemically) and produces only water as a product. In contrast, hydrocarbon energy carriers inevitably produce CO2, contributing to global warming. While CO2 capture may prove feasible in large stationary applications, implementing it in transportation and mobile applications is a daunting challenge. Thus a zero-emission energy carrier like hydrogen is especially needed in these cases. Use of H2 as an energy carrier also brings new challenges such as safe handling of compressed hydrogen and implementation of new transport, storage, and delivery processes and infrastructure. With current storage technologies, hydrogen's energy per volume is very low compared to other automobile fuels. High density storage of compressed hydrogen requires combinations of high pressure and/or low temperature that are not very practical. An alternative for storage is use of solid light weight hydrogenous material systems which have long durability, good adsorption properties and high activity. Substantial research has been conducted on carbon materials like activated carbon, carbon nanofibers, and carbon nanotubes due to their high theoretical hydrogen capacities. However, the theoretical values have not been achieved, and hydrogen uptake capacities in these materials are below 10 wt. %. In this thesis we investigated the use of silicon for hydrogen generation. Hydrogen generation via water oxidation of silicon had been ignored due to slow reaction kinetics. We hypothesized that the hydrogen generation rate could be improved by using high surface area silicon nanoparticles. Our laser-pyrolysis-produced nanoparticles showed surprisingly rapid hydrogen generation and high hydrogen yield, exceeding the theoretical maximum of two moles of H2 per mole of Si. We compare our silicon nanoparticles (˜10nm diameter) with commercial silicon nanopowder (<100nm diameter) and ball-milled silicon powder (325 mesh). The increase in rate upon decreasing the particle size to 10 nm was even greater than would be expected based upon the increase in surface area. While specific surface area increased by a factor of 6 in going from <100 nm to ˜10 nm particles, the hydrogen production rate increased by a factor of 150. However, in all cases, silicon requires a base (e.g. NaOH, KOH, hydrazine) to catalyze its reaction with water. Metal hydrides are also promising hydrogen storage materials. The optimum metal hydride would possess high hydrogen storage density at moderate temperature and pressure, release hydrogen safely and controllably, and be stable in air. Alkali metal hydrides have high hydrogen storage density, but exhibit high uncontrollable reactivity with water. In an attempt to control this explosive nature while maintaining high storage capacity, we mixed our silicon nanoparticles with the hydrides. This has dual benefits: (1) the hydride- water reaction produces the alkali hydroxide needed for base-catalyzed silicon oxidation, and (2) dilution with 10nm coating by, the silicon may temper the reactivity of the hydride, making the process more controllable. Initially, we analyzed hydrolysis of pure alkali metal hydrides and alkaline earth metal hydrides. Lithium hydride has particularly high hydrogen gravimetric density, along with faster reaction kinetics than sodium hydride or magnesium hydride. On analysis of hydrogen production we found higher hydrogen yield from the silicon nanoparticle—metal hydride mixture than from pure hydride hydrolysis. The silicon-hydride mixtures using our 10nm silicon nanoparticles produced high hydrogen yield, exceeding the theoretical yield. Some evidence of slowing of the hydride reaction rate upon addition of silicon nanoparticles was observed.

Unusual Metals in Galactic Center Stars

NASA Astrophysics Data System (ADS)

Hensley, Kerry

2018-03-01

Far from the galactic suburbs where the Sun resides, a cluster of stars in the nucleus of the Milky Way orbits a supermassive black hole. Can chemical abundance measurements help us understand the formation history of the galactic center nuclear star cluster?Studying Stellar PopulationsMetallicity distributions for stars in the inner two degrees of the Milky Way (blue) and the central parsec (orange). [Do et al. 2018]While many galaxies host nuclear star clusters, most are too distant for us to study in detail; only in the Milky Way can we resolve individual stars within one parsec of a supermassive black hole. The nucleus of our galaxy is an exotic and dangerous place, and its not yet clear how these stars came to be where they are were they siphoned off from other parts of the galaxy, or did they form in place, in an environment rocked by tidal forces?Studying the chemical abundances of stars provides a way to separate distinct stellar populations and discern when and where these stars formed. Previous studies using medium-resolution spectroscopy have revealed that many stars within the central parsec of our galaxy have very high metallicities possibly higher than any other region of the Milky Way. Can high-resolution spectroscopy tell us more about this unusual population of stars?Spectral Lines on DisplayTuan Do (University of California, Los Angeles, Galactic Center Group) and collaborators performed high-resolution spectroscopic observations of two late-type giant starslocated half a parsec from the Milky Ways supermassive black hole.Comparison of the observed spectra of the two galactic center stars (black) with synthetic spectra with low (blue) and high (orange) [Sc/Fe] values. Click to enlarge. [Do et al. 2018]In order to constrain the metallicities of these stars, Do and collaborators compared the observed spectra to a grid of synthetic spectra and used a spectral synthesis technique to determine the abundances of individual elements. They found that while one star is only slightly above solar metallicity, the other is likely more than four times as metal-rich as the Sun.The features in the observed and synthetic spectra generally matched well, but the absorption lines of scandium, vanadium, and yttrium were consistently stronger in the observed spectra than in the synthetic spectra. This led the authors to conclude that these galactic center stars are unusually rich in these metals trace elements that could reveal the formation history of the galactic nucleus.Old Stars, New Trends?Scandium to iron ratio versusiron abundance for stars in the disk of the Milky Way (blue) and the stars in this sample (orange). The value reported for this sample is a 95% lower limit. [Do et al. 2018]For stars in the disk of the Milky Way, the abundance of scandium relative to iron tends to decrease as the overall metallicity increases, but the stars investigated in this study are both iron-rich and anomalously high in scandium. This hints that the nuclear star cluster might represent a distinct stellar population with different metallicity trends.However, its not yet clear what could cause the elevated abundances of scandium, vanadium, and yttrium relative to other metals. Each of these elements is linked to a different source; scandium and vanadium are mainly produced in Type II and Type Ia supernovae, respectively, while yttrium is likely synthesized in asymptotic giant branch stars. Future observations of stars near the center of the Milky Way may help answer this question and further constrain the origin of our galaxys nuclear star cluster.CitationTuan Do et al 2018 ApJL 855 L5. doi:10.3847/2041-8213/aaaec3

Hydrogen absorption properties of Mg-Ni alloys prepared by bulk mechanical alloying

NASA Astrophysics Data System (ADS)

Kuji, Toshiro

2001-04-01

The thermodynamic properties of the hydrides of Mg2-xNi (x=0-0.5) alloys produced by bulk mechanical alloying (BMA) were determined from pressure-composition (PC) isotherms for absorption over temperatures from 623 to 423 K. The vant Hoff plot for the plateau pressures of isotherms clearly indicated the existence of high and low temperature hydrides with different entropy and enthalpy for hydride formation. It was found that both the entropy and enthalpy values for the high temperature hydride were more negative than for the low temperature hydride. The phase transition temperature was 525 K for Mg2.0Ni and decreased while increasing the value of x. This allotropic transformation was well confirmed by in-situ XRD observations from RT to 673 K under hydrogen atmosphere or in vacuum.

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

Low-valent group 14 element hydride chemistry: towards catalysis.

PubMed

Hadlington, Terrance J; Driess, Matthias; Jones, Cameron

2018-06-05

The chemistry of group 14 element(ii) hydride complexes has rapidly expanded since the first stable example of such a compound was reported in 2000. Since that time it has become apparent that these systems display remarkable reactivity patterns, in some cases mimicking those of late transition-metal (TM) hydride compounds. This is especially so for the hydroelementation of unsaturated organic substrates. Recently, this aspect of their reactivity has been extended to the use of group 14 element(ii) hydrides as efficient, "TM-like" catalysts in organic synthesis. This review will detail how the chemistry of these hydride compounds has advanced since their early development. Throughout, there is a focus on the importance of ligand effects in these systems, and how ligand design can greatly modify a coordinated complex's electronic structure, reactivity, and catalytic efficiency.

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.

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.

Microstructural studies of hydrogen damage in metastable stainless steels. Ph.D. Thesis

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

Chen, S.

1994-12-31

The primary objective of this dissertation is to determine the role of microstructure in hydrogen-induced damage in austenitic stainless steels. Specific attention was focused on the interactions between hydrogen and the austenitic grain, twin boundaries and the matrix, and the associated phase transformations. An experimental program of research was conducted to determine the phase transformation and cracking path in hydrogen charged stainless steels. Normal-purity AISI 304 (Fe18CrYNi) and high-purity 305 (Fe18Cr12Ni) solution-annealet stainless steels were examined. The steels were cathodically charged with hydrogen at 1, 10 and 100 mA/sq cm at room temperature for 5 min. to 32 hours, inmore » an 1N H2SO4 solution with 0.25 g/l of NaAsO2 added as a hydrogen recombination poison. Resultant changes in microstructure and hydrogen damage due to charging and subsequent room temperature aging were studied by x-ray diffraction, optical microscope (in the Nomarski mode), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). A new phase in 305 stainless steel was observed, and was identified as an epsilon(*) (hcp) hydride due to hydrogen charging. Two new phases in 304 stainless steel were found as gamma(*) (fcc) and epsilon(*) hydrides from hydrogen charging. The hydride formation mechanisms during charging were: (1) gamma yields gamma(*) hydride and (2) gamma yields epsilon yields epsilon(*) hydride. These hydrides are unstable and decomposed during room temperature aging in air. The decomposition mechanisms were: (1) epsilon(*) hydride (hcp) yields expanded epsilon (hcp) phase yields a (bcc) phase; (2) gamma(*) hydride yields gamma phase. The grain and twin boundary cracks were the results of charging and identified as the preferred cracking sites. Transgranular crack initiation and growth accompanied the decomposition of hydrides and were controlled by hydrogen outgassing during room temperature aging.« less

The Current Status of Hydrogen Storage Alloy Development for Electrochemical Applications

PubMed Central

Young, Kwo-hsiung; Nei, Jean

2013-01-01

In this review article, the fundamentals of electrochemical reactions involving metal hydrides are explained, followed by a report of recent progress in hydrogen storage alloys for electrochemical applications. The status of various alloy systems, including AB5, AB2, A2B7-type, Ti-Ni-based, Mg-Ni-based, BCC, and Zr-Ni-based metal hydride alloys, for their most important electrochemical application, the nickel metal hydride battery, is summarized. Other electrochemical applications, such as Ni-hydrogen, fuel cell, Li-ion battery, air-metal hydride, and hybrid battery systems, also have been mentioned. PMID:28788349

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

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

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.

LEWIS ACID CATALYZED FORMATION OF TETRAHYDROPYRANS IN IONIC LIQUID

EPA Science Inventory

Tetrahydropyrans are integral moieties in innumerable natural products and have inspired the development of a variety of different methodologies. A Prins-type cyclization involving the coupling of a homoallylic alcohol and an aldehyde in the presence of catalytic scandium triflat...

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.

The increase in fatigue crack growth rates observed for Zircaloy-4 in a PWR environment

NASA Astrophysics Data System (ADS)

Cockeram, B. V.; Kammenzind, B. F.

2018-02-01

Cyclic stresses produced during the operation of nuclear reactors can result in the extension of cracks by processes of fatigue. Although fatigue crack growth rate (FCGR) data for Zircaloy-4 in air are available, little testing has been performed in a PWR primary water environment. Test programs have been performed by Gee et al., in 1989 and Picker and Pickles in 1984 by the UK Atomic Energy Authority, and by Wisner et al., in 1994, that have shown an enhancement in FCGR for Zircaloy-2 and Zircaloy-4 in high-temperature water. In this work, FCGR testing is performed on Zircaloy-4 in a PWR environment in the hydrided and non-hydrided condition over a range of stress-intensity. Measurements of crack extension are performed using a direct current potential drop (DCPD) method. The cyclic rate in the PWR primary water environment is varied between 1 cycle per minute to 0.1 cycle per minute. Faster FCGR rates are observed in water in comparison to FCGR testing performed in air for the hydrided material. Hydrided and non-hydrided materials had similar FCGR values in air, but the non-hydrided material exhibited much lower rates of FCGR in a PWR primary water environment than for hydrided material. Hydrides are shown to exhibit an increased tendency for cracking or decohesion in a PWR primary water environment that results in an enhancement in FCGR values. The FCGR in the PWR primary water only increased slightly with decreasing cycle frequency in the range of 1 cycle per minute to 0.1 cycle per minute. Comparisons between the FCGR in water and air show the enhancement from the PWR environment is affected by the applied stress intensity.

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

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.

Effect of hydrogen on fatigue crack propagation in vanadium

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

Chung, D.W.; Stoloff, N.S.

The influence of hydrogen on fatigue crack propagation in unalloyed vanadium and several hydrogen-charged vanadium alloys has been investigated. The Paris--Erdogan equation, da/dN = C(..delta..K)/sup m/, was approximately obeyed for all alloys. Crack growth rates were lowest in vanadium and dilute vanadium-hydrogen alloys, and were not very sensitive to volume fraction of hydrides in more concentrated alloys. The crack growth exponent, m, is inversely proportional to the cyclic strain hardening rate, n', and the rate constant C is inversely proportional to the square of the ultimate tensile stress, sigma/sub UTS/: metallographic examination showed hydride reorientation and growth in the originallymore » hydrided alloys. No stress-induced hydrides were observed in V-H solid-solution alloys. Fractures in hydrided materials exhibited cleavage-like features, while striations were noted in unalloyed vanadium and dilute solid-solution alloys.« less

Effect of hydrogen on fatigue crack propagation in vanadium

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

Chung, D.W.; Stoloff, N.S.

The influence of hydrogen on fatigue crack propagation in unalloyed vanadium and several hydrogen-charged vanadium alloys has been investigated. The Paris--Erdogan equation, da/dN = C(..delta..K)/sup m/, was approximately obeyed for all alloys. Crack growth rates were lowest in vanadium and dilute vanadium--hydrogen alloys, and were not very sensitive to volume fraction of hydrides in more concentrated alloys. The crack growth exponent, m, is inversely proportional to the cyclic strain hardening rate, n', and the rate constant C is inversely proportional to the square of the ultimate tensile stress, sigma/sub UTS/: metallographic examination showed hydride reorientation and growth in the originallymore » hydrided alloys. No stress-induced hydrides were observed in V--H solid-solution alloys. Fractures in hydrided materials exhibited cleavage-like features, while striations were noted in unalloyed vanadium and dilute solid-solution alloys.« 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

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.

Wafer-Fused Orientation-Patterned GaAs

DTIC Science & Technology

2008-02-13

frequencies utilizing existing industrial foundries. 15. SUBJECT TERMS Orientation-patterned Gallium Arsenide, hydride vapor phase epitaxy, quasi-phase... Gallium Arsenide, hydride vapor phase epitaxy, quasi-phase-matching, nonlinear frequency conversion 1. INTRODUCTION Quasi-phase-matching (QPM)1...and E. Lallier, “Second harmonic generation of CO2 laser using thick quasi-phase-matched GaAs layer grown by hydride vapour phase epitaxy

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.

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.

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.

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.

Creation of Y2Ti2O7 nanoprecipitates to strengthen the Fe-14Cr-3Al-2W steels by adding Ti hydride and Y2O3 nanoparticles

NASA Astrophysics Data System (ADS)

Wang, Linbo; Bai, Zhonglian; Shen, Hailong; Wang, Chenxi; Liu, Tong

2017-05-01

In order to prohibit the formation of large Y-Al-O precipitates, Ti hydride nanoparticles (NPs) were prepared and used to replace Ti as raw particles to fabricate the oxide dispersion strengthened (ODS) Fe-14Cr-3Al-2W-0.35Y2O3 steels by mechanical alloying (MA) and hot isostatic pressing (HIP). As the content of Ti hydride increases from 0.1 to 0.5 and 1.0 wt%, the oxide nanoprecipitates in the ODS steels changes from Y3Al5O12 phase to Y2Ti2O7 phase (semicoherent with the matrix), and the particle size is successfully reduced. The tensile strength of the ODS steel increases remarkably with increasing Ti hydride content. The sample with 1.0 wt% Ti hydride exhibits a high strength of 1049 MPa at 25 °C and 278 MPa at 700 °C. The creation of Y2Ti2O7 nanoprecipitates by adding Ti hydride NPs opens a new way to control the structure and size of the oxide precipitates in the ODS steels.

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.

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

Insights into the mantle geochemistry of scandium from a meta-analysis of garnet data

NASA Astrophysics Data System (ADS)

Chassé, Mathieu; Griffin, William L.; Alard, Olivier; O'Reilly, Suzanne Y.; Calas, Georges

2018-06-01

The meta-analysis of about 13,000 analyses of scandium content in garnet grains shows that, below the spinel-garnet transition, this phase carries about three-quarters of the Sc budget of the mantle, indicating its control on Sc mobility. The Sc content of garnets in mafic rocks is low, due to a dilution effect resulting from their high modal content in garnet. Garnets from ultramafic rocks exhibit a wider range of Sc concentrations. We assess the relative influence of thermobarometry, crystal chemistry and fluid-related events on the distribution of Sc in garnet from such rocks to improve the tracking of geochemical processes in the mantle. Pressure and temperature of equilibration in the mantle are second-order factors influencing the Sc content of garnet, while crystal chemistry, in particular Cr/Cr+Al and Ca/Ca+Mg, is the main parameter controlling the compatibility of Sc. Scandium is incorporated in both X and Y sites of Cr-Ca-rich garnets, resulting in a behaviour intermediate between rare-earth elements, incorporated in the X site, and trivalent transition elements, occupying the Y site. This affinity for both sites results in a mild compatibility of Sc in the garnet stability field of the mantle; hence Sc concentration in garnet increases with melt extraction and can be reduced by silicate-melt metasomatism. In contrast, metasomatism by volatile-rich fluids increases the Sc concentration in garnet. The control of garnet on the compatibility of Sc in deep lithospheric rocks demonstrates the potential of using Sc to track the conditions of formation of magmas and their residual rocks, as well as the origin and nature of metasomatic fluids.

Luminescence behaviour and deposition of Sc2O3 thin films from scandium(III) acetylacetonate at ambient pressure

NASA Astrophysics Data System (ADS)

Dixon, Sebastian C.; Jiamprasertboon, Arreerat; Carmalt, Claire J.; Parkin, Ivan P.

2018-05-01

Scandium(III) oxide thin film deposition has been historically difficult to achieve without the use of vacuum-based or wet chemical systems due to precursor limitations of low vapour pressure or ambient instability. In this letter, the adoption of aerosol-assisted delivery of scandium(III) acetylacetonate has enabled the chemical vapour deposition of polycrystalline and amorphous Sc2O3 thin films at ambient pressure with high growth rates (ca. 500 nm h-1). The scandia films were intrinsically highly photoluminescent, exhibiting broad emission bands centred at 3.6 and 3.0 eV, which increased significantly in intensity upon aerobic annealing, accompanying a transition from amorphous to crystalline, while bands appearing at 2.1 and 2.3 eV seemed to occur only in the crystalline films. In addition, both amorphous and crystalline scandia films exhibited blue-green vibronic fine structure between 2.3 and 3.2 eV attributed to the electronic transition B→κ Σ+ 2 Σ+ in surface ⋯ O - ⋯ O - S c = O groups and split by a vibrational mode observed at 920 ± 60 cm - 1 by infrared spectroscopy. Band gaps of amorphous and crystalline Sc2O3 were determined to be 5.3 and 5.7 eV, respectively via diffuse reflectance. All films had high refractive indices, varying between 1.8 and 2.0 at 400 nm depending on film thickness and carrier gas used in the deposition; film thicknesses less than ca. 300 nm were observed to have a strong influence on the refractive index measured, while there was little variation for films thicker than this. The synthesis process itself is exceedingly low-cost and facile thus promising streamlined industrial scalability.

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.

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.

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 improve, ductility of recrystallized Zircaloy-2 cladding with inner liner with such hydrogen content.

40 CFR 421.271 - Specialized definitions.

Code of Federal Regulations, 2013 CFR

2013-07-01

... AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Primary Rare Earth Metals.... (b) The term rare earth metals refers to the elements scandium, yttrium, and lanthanum to lutetium, inclusive. (c) The term mischmetal refers to a rare earth metal alloy comprised of the natural mixture of...

40 CFR 421.271 - Specialized definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

... AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Primary Rare Earth Metals.... (b) The term rare earth metals refers to the elements scandium, yttrium, and lanthanum to lutetium, inclusive. (c) The term mischmetal refers to a rare earth metal alloy comprised of the natural mixture of...

40 CFR 421.271 - Specialized definitions.

Code of Federal Regulations, 2012 CFR

2012-07-01

... AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Primary Rare Earth Metals.... (b) The term rare earth metals refers to the elements scandium, yttrium, and lanthanum to lutetium, inclusive. (c) The term mischmetal refers to a rare earth metal alloy comprised of the natural mixture of...

40 CFR 421.271 - Specialized definitions.

Code of Federal Regulations, 2011 CFR

2011-07-01

... AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Primary Rare Earth Metals.... (b) The term rare earth metals refers to the elements scandium, yttrium, and lanthanum to lutetium, inclusive. (c) The term mischmetal refers to a rare earth metal alloy comprised of the natural mixture of...

High performance AlScN thin film based surface acoustic wave devices with large electromechanical coupling coefficient

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

Wang, Wenbo; He, Xingli; Ye, Zhi, E-mail: yezhi@zju.edu.cn, E-mail: jl2@bolton.ac.uk

AlN and AlScN thin films with 27% scandium (Sc) were synthesized by DC magnetron sputtering deposition and used to fabricate surface acoustic wave (SAW) devices. Compared with AlN-based devices, the AlScN SAW devices exhibit much better transmission properties. Scandium doping results in electromechanical coupling coefficient, K{sup 2}, in the range of 2.0% ∼ 2.2% for a wide normalized thickness range, more than a 300% increase compared to that of AlN-based SAW devices, thus demonstrating the potential applications of AlScN in high frequency resonators, sensors, and high efficiency energy harvesting devices. The coupling coefficients of the present AlScN based SAW devices are muchmore » higher than that of the theoretical calculation based on some assumptions for AlScN piezoelectric material properties, implying there is a need for in-depth investigations on the material properties of AlScN.« less

Mid-Infrared Spectroscopy Analysis of the Effects of Erbium, Chromium:Yattrium-Scandium-Gallium-Garnet (Er,Cr:YSGG) Laser Irradiation on Bone Mineral and Organic Components.

PubMed

Benetti, Carolina; Ana, Patricia Aparecida; Bachmann, Luciano; Zezell, Denise Maria

2015-12-01

The effects of varying the energy density of a high-intensity erbium, chromium: yttrium-scandium-gallium-garnet (Er,Cr:YSGG) laser on the mineral and organic components of bone tissue were evaluated using Fourier transform infrared spectroscopy. Bone samples obtained from the tibias of rabbits were irradiated with five energy densities (3, 6, 8, 12, and 15 J/cm(2)), and the effects on the carbonate to phosphate ratio and in the organic components were compared with those of nonirradiated samples. The increased temperature during the laser irradiation was also measured using infrared thermography to relate the observed spectral changes to the laser thermal effects. The analyses of the infrared spectra suggests that the irradiation with Er,Cr:YSGG promoted changes in bone tissue in both the mineral and organic components that depend on the laser energy density, pointing to the importance of using the proper energy density in clinical procedures.

Yb-doped mixed-sesquioxide films grown by pulsed laser deposition

NASA Astrophysics Data System (ADS)

Prentice, Jake J.; Grant-Jacob, James A.; Shepherd, David P.; Eason, Robert W.; Mackenzie, Jacob I.

2018-06-01

Growth and characterization of compositionally tuned, ytterbium-doped mixed lutetium-scandium oxide, and pure lutetia and scandia crystalline films are presented. Pulsed laser deposition was employed to grow these sesquioxide films, of thicknesses up to 20 μm, on (0 0 0 1)-sapphire substrates. By varying the atomic ratio of lutetium to scandium in the target, the lattice parameter of the resulting films could be tuned to match that of the single-crystal c-cut sapphire substrate and thereby achieve a lattice mismatch of <0.1%. Optimization of growth parameters led to a reduction of undesirable particulates and scattering points within the film. X-ray diffraction measurements show (2 2 2)-orientated epitaxial growth with crystallinity comparable to bulk crystals. Through pole figure and electron-backscatter imaging measurements, it was found that two inverted cubic lattice orientations grow with micron-scaled domains. Growth of these lattice-matched mixed sesquioxides paves the way for fabrication of high-quality waveguides suitable for generation of ultrashort laser pulses.

Labeling of DOTA-conjugated HPMA-based polymers with trivalent metallic radionuclides for molecular imaging.

PubMed

Eppard, Elisabeth; de la Fuente, Ana; Mohr, Nicole; Allmeroth, Mareli; Zentel, Rudolf; Miederer, Matthias; Pektor, Stefanie; Rösch, Frank

2018-02-27

In this work, the in vitro and in vivo stabilities and the pharmacology of HPMA-made homopolymers were studied by means of radiometal-labeled derivatives. Aiming to identify the fewer amount and the optimal DOTA-linker structure that provides quantitative labeling yields, diverse DOTA-linker systems were conjugated in different amounts to HPMA homopolymers to coordinate trivalent radiometals Me(III)* = gallium-68, scandium-44, and lutetium-177. Short linkers and as low as 1.6% DOTA were enough to obtain labeling yields > 90%. Alkoxy linkers generally exhibited lower labeling yields than alkane analogues despite of similar chain length and DOTA incorporation rate. High stability of the radiolabel in all examined solutions was observed for all conjugates. Labeling with scandium-44 allowed for in vivo PET imaging and ex vivo measurements of organ distribution for up to 24 h. This study confirms the principle applicability of DOTA-HPMA conjugates for labeling with different trivalent metallic radionuclides allowing for diagnosis and therapy.

Evaluation of the Benjamin type proportional counter for absolute neutron spectrometry

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

Taeb, M.

1985-01-01

This evaluation has shown that the major sources of uncertainty in experimental measurements with a Benjamin detector are: (1) detector pressure, (2) hydrogen gas purity, (3) detector calibration, and (4) operating voltage. To test these operational parameters, neutron spectra were measured at the University of Missouri Research Reactor (MURR) for silicon, scandium, iron, and bismuth filtered beams and angular penetration data through an 20.3 cm water slab. Results were then critically compared with theoretical calculations and with data from other spectrometer systems in regions of energy overlap. Neutron spectra having relatively small contributions from neutrons with energies higher than themore » energy range of the Benjamin spectrometer (at a specific pressure) generally exhibit excellent results. This is particularly true for the silicon filter (which produces two quasi-monoenergetic peaks at 55 keV and 144 keV) and the scandium filter (which creates a spectrum which decreases with increasing energy). For those spectra exhibiting relatively larger high energy neutron components, the results are less satisfying.« less

Effects of an erbium, chromium: yttrium, scandium, gallium, garnet laser on mucocutanous soft tissues.

PubMed

Rizoiu, I M; Eversole, L R; Kimmel, A I

1996-10-01

Lasers are effective tools for soft tissue surgery. The erbium, chromium: yttrium, scandium, gallium, garnet laser is a new system that incorporates an air-water spray. This study evaluates the cutting margins of this laser and compares healing with laser and conventional scalpel and punch biopsy-induced wounds. New Zealand white rabbits were divided into serial sacrifice groups; the tissues were grossly and microscopically analyzed after laser and convential steel surgical wounding. Wound margins were found to show minimal edge coagulation artifact and were 20 to 40 mm in width. Laser wounds showed minimal to no hemorrhage and re-epithelialization and collagenization were found to occur by day 7 in both laser and conventional groups. The new laser system is an effective soft tissue surgical device; wound healing is comparable to that associated with surgical steel wounds. The minimal edge artifact observed with this laser system should allow for the procurement of diagnostic biopsy specimens.

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 are ∼2 kcal/mol higher than for the Ir complexes, despite the fact that the energy difference between the olefin hydride ground state and the agostic alkyl structure is ∼4 kcal/mol larger for Ir than for Rh. This feature, together with the high barrier for interchange of the top and bottom faces of the complexes, is proposed to arise from the unique coordination geometry of the agostic complexes and the strong preference for a cis-divacant octahedral geometry in four-coordinate intermediates. © 2011 American Chemical Society

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.

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

Schwarz, R.B.; Bach, H.T.; Harms, U.

We used a resonant-ultrasound-spectroscopy technique to measure the three independent elastic constants of PdH{sub x}, PdD{sub x}, and PdT{sub x} single crystals at 300 K. For 0.1x0.62 our PdH{sub x} crystals are two-phase mixtures of coherent {alpha} and {beta} hydride phases. For increasing x in this range, C{sub 44} decreases monotonically whereas C'=12(C11-C12) has a concave parabolic dependence. This difference is because C' is softened by an anelastic relaxation resulting from acoustic-stress-induced changes in the shape of the coherent lenticular-shape precipitates ({beta}-hydride precipitates in {alpha}-hydride matrix and {alpha}-hydride precipitates in {beta}-hydride matrix). In the {beta}-phase C' and C{sub 44} decreasemore » with increasing hydrogen (or deuterium or tritium) content. Furthermore, C' exhibits a strong isotope effect whereas C{sub 44} does not. This effect is attributed to differences in the excitation of optical phonons in Pd-H, Pd-D and Pd-T.« less

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.

Hydrogen interactions with metals

NASA Technical Reports Server (NTRS)

Mclellan, R. B.; Harkins, C. G.

1975-01-01

Review of the literature on the nature and extent of hydrogen interactions with metals and the role of hydrogen in metal failure. The classification of hydrogen-containing systems is discussed, including such categories as covalent hydrides, volatile hydrides, polymeric hydrides, and transition metal hydride complexes. The use of electronegativity as a correlating parameter in determining hydride type is evaluated. A detailed study is made of the thermodynamics of metal-hydrogen systems, touching upon such aspects as hydrogen solubility, the positions occupied by hydrogen atoms within the solvent metal lattice, the derivation of thermodynamic functions of solid solutions from solubility data, and the construction of statistical models for hydrogen-metal solutions. A number of theories of hydrogen-metal bonding are reviewed, including the rigid-band model, the screened-proton model, and an approach employing the augmented plane wave method to solve the one-electron energy band problem. Finally, the mechanism of hydrogen embrittlement is investigated on the basis of literature data concerning stress effects and the kinetics of hydrogen transport to critical sites.

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

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 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.

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.

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

Electrochemical hydride generation for the simultaneous determination of hydride forming elements by inductively coupled plasma-atomic emission spectrometry

NASA Astrophysics Data System (ADS)

Bolea, E.; Laborda, F.; Castillo, J. R.; Sturgeon, R. E.

2004-04-01

Simultaneous measurements of As, Sb, Se, Sn and Ge were performed by inductively coupled plasma atomic emission spectrometry following their electrochemical hydride generation. An electrochemical hydride generator based on a concentric arrangement with a porous cathode, working in a continuous flow mode was used. The effects of sample flow rate, applied current and electrolytic solution concentration on response were studied and their influence on the mechanisms of hydride generation discussed. Four materials, particulate lead, reticulated vitreous carbon (RVC), silver and amalgamated silver were tested as cathode materials. The best results were achieved with particulate lead and RVC cathodes, wherein generation efficiencies higher than 80% were estimated for most of the analytes. In general, limits of detection between 0.1 and 3.6 ng ml -1 and a precision better than 5% were achieved using a lead cathode. The analysis of a marine sediment reference material (PACS-2, NRC) showed good agreement with the certified values for As and Se.

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.

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.

Cryo-Milling and the Hydrogen Storage Properties of NaAlH4

NASA Astrophysics Data System (ADS)

Feller, Kevin; Dobbins, Tabbetha

2013-03-01

High energy ball milling of metal hydrides is a common way to both introduce catalysts (e.g. TiCl3) and to simultaneously increase the surface area. Both catalysis and increased surface area improve hydrogen storage capacity of the material. Nanostructuring of hydrides by depositing them into mesoporous templates (such as anodized alumina, MOFs, and SBA-15) has become a common way to increase surface area. However, the mesoporous template does not add hydrogen storage capacity--and thus, tends to decreased overall storage weight percent for the nanostructured hydride material. As with most materials, hydrides become brittle at low temperatures and will tend to fracture more readily. We will process Sodium Aluminum Hydride (NaAlH4) using cryogenic high energy ball milling using an in-house modified chamber SPEX Certiprep M8000 mixer/mill in order to gain a nanostructured hydride without mesoporous template material. Details of the modified mixer mill design will be presented. Ultimately, our planned future work is to study the resultant material using x-ray diffraction (Scherrer method for crystallite size), absorption/desorption temperature programmed desorption (TPD), and ultrasmall-angle x-ray scattering (USAXS) microstructural quantification to understand the role of cryomilling on enhancing the material's ability to store (and release) hydrogen.

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

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.

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

Zhu Tangkui, E-mail: zhutangkui@sohu.com; Li, Miaoquan, E-mail: honeymli@nwpu.edu.cn

Effect of hydrogen content on the lattice parameter of Ti-6Al-4V alloy has been investigated by X-ray diffraction. The experimental results show that the solution of hydrogen in the Ti-6Al-4V alloy affects significantly on the lattice parameters of {alpha}, {beta} and {delta} phases, especially the {beta} phase. Furthermore, the critical hydrogen content of {delta} hydride formation for Ti-6Al-4V alloy is 0.385 wt.%. When the hydrogen content is lower than the critical hydrogen content, the {delta} hydride cannot precipitate and the lattice parameter ({alpha}) of {beta} phase linearly increases with the increasing of hydrogen content. When the hydrogen content is higher thanmore » the critical hydrogen content, the {delta} hydride precipitates and the lattice parameter ({alpha}) of {beta} phase varies inconspicuously with hydrogen content. In addition, the effects of lattice variations and {delta} hydride formation on microstructure are discussed. The {alpha}/{beta} interfaces of lamellar transformed {beta} phase become fuzzy with the increasing of hydrogen content because of the lattice expansion of {beta} phase. Compared with that of the Ti-6Al-4V alloy at low hydrogen content ({<=} 0.385 wt.%), the contrasts of primary {alpha} phase and transformed {beta} phase of Ti-6Al-4V alloy at high hydrogen content ({>=} 0.385 wt.%) were completely reversed due to the formation of {delta} hydride. - Research Highlights: {yields} A novel method for determining {delta} hydride in Ti-6Al-4V alloy is presented. {yields} The critical hydrogen content of {delta} hydride formation is 0.385 wt.%. {yields} The lattice parameter of {beta} phase can be expressed as follows: a=0.323(1+9.9x10{sup -2}C{sub H}) . {yields} Precipitation of {delta} hydride has a significant influence on the microstructure. {yields} The {alpha}/{beta} interfaces of transformed {beta} phase became fuzzy in the hydrogenated alloy.« less

Influence of uranium hydride oxidation on uranium metal behaviour

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

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

2013-07-01

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

SCANDIUM TRIFLATE CATALYZED IN SITU PRINS-TYPE CYCLIZATION: FORMATIONS OF 4-TETRAHYDROPYRANOLS AND ETHERS. (R822668)

EPA Science Inventory

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

Temperature dependence of the 1.06-microm stimulated emission cross section of neodymium in YAG and in GSGG.

PubMed

Rapaport, Alexandra; Zhao, Shengzhi; Xiao, Guohua; Howard, Andrew; Bass, Michael

2002-11-20

A linear temperature dependence between -70 degrees C and +70 degrees C is reported for the peak stimulated emission cross section of Nd3+ ions in both yttrium aluminum garnet (YAG) and gadolinium scandium gallium garnet (GSGG).

Carbon quantum dots and a method of making the same

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

Zidan, Ragaiy; Teprovich, Joseph A.; Washington, Aaron L.

The present invention is directed to a method of preparing a carbon quantum dot. The carbon quantum dot can be prepared from a carbon precursor, such as a fullerene, and a complex metal hydride. The present invention also discloses a carbon quantum dot made by reacting a carbon precursor with a complex metal hydride and a polymer containing a carbon quantum dot made by reacting a carbon precursor with a complex metal hydride.

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.

Method of producing hydrogen

DOEpatents

Bingham, Dennis N.; Klingler, Kerry M.; Wilding, Bruce M.; Zollinger, William T.

2006-12-26

A method of producing hydrogen is disclosed and which includes providing a first composition; providing a second composition; reacting the first and second compositions together to produce a chemical hydride; providing a liquid and reacting the chemical hydride with the liquid in a manner to produce a high pressure hydrogen gas and a byproduct which includes the first composition; and reusing the first composition formed as a byproduct in a subsequent chemical reaction to form additional chemical hydride.

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.

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.

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

Reduction of Carbon Monoxide. Past Research Summary

DOE R&D Accomplishments Database

Schrock, R. R.

1982-01-01

Research programs for the year on the preparation, characterization, and reactions of binuclear tantalum complexes are described. All evidence to date suggest the following of these dimeric molecules: (1) the dimer does not break into monomers under mild conditions; (2) intermolecular hydride exchange is not negligible, but it is slow; (3) intermolecular non-ionic halide exchange is fast; (4) the ends of the dimers can rotate partially with respect to one another. The binuclear tantalum hydride complexes were found to react with carbon monoxide to give a molecule which is the only example of reduction of CO by a transition metal hydride to give a complex containing a CHO ligand. Isonitrides also reacted in a similar manner with dimeric tantalum hydride. (ATT)

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 means of digital image processing, so as to understand the influence of the hydride microstructure on fracture toughness, at the various test temperatures. Crack growth occurred through a microstructure which varied within the thickness of the thin-sheet Zircaloy-4 such that the hydrogen concentration and the radial hydride content decreased with increasing distance from the hydride blister. At 25°C, the fracture toughness was sensitive to the changes in hydride microstructure, such that the toughness KJi decreased from 39 MPa√m to 24 MPa√m with increasing hydrogen content and increasing the fraction of radial hydrides. The hydride particles present in the Zircaloy-4 substrate fractured ahead of the crack tip, and crack growth occurred by linking the crack-tip with the next hydride-induced primary void ahead of it. Unstable crack growth was observed at 25°C prior to any stable crack growth in the specimens where the hydrogen content was the highest. At 375°C as well as in most cases at 300°C, the hydride particles were resistant to cracking and the resistance to crack-growth initiation was very high. As a result, for this bend test procedure, crack extension was solely due to crack-tip blunting instead of crack growth in all tests at 375°C and in most cases at 300°C. The lower bound for fracture toughness at these temperatures, the parameter KJPmax, had values of K JPmax˜54MPa√m at both 300°C and 375°C. For cases where stable crack growth occurred at 300°C, the fracture toughness was K Ji˜58MPa√m and the tearing modulus was twice as high as that at 25°C. It is believed that the failure of hydrided Zircaloy-4 thin-wall cladding can be predicted using fracture mechanics analyses when failure occurs by crack growth. This failure mechanism was observed to occur in all cases at 25°C and in some cases at 300°C. However, at more elevated temperatures, such as 375°C, failure will likely occur by a mechanism other than crack growth, possibly by an imperfection-induced shear instability.

Density functional theory mechanistic study of the reduction of CO2 to CH4 catalyzed by an ammonium hydridoborate ion pair: CO2 activation via formation of a formic acid entity.

PubMed

Wen, Mingwei; Huang, Fang; Lu, Gang; Wang, Zhi-Xiang

2013-10-21

Density functional theory computations have been applied to gain insight into the CO2 reduction to CH4 with Et3SiH, catalyzed by ammonium hydridoborate 1 ([TMPH](+)[HB(C6F5)3](-), where TMP = 2,2,6,6-tetramethylpiperidine) and B(C6F5)3. The study shows that CO2 is activated through the concerted transfer of H(δ+) and H(δ-) of 1 to CO2, giving a complex (IM2) with a well-formed HCOOH entity, followed by breaking of the O-H bond of the HCOOH entity to return H(δ+) to TMP, resulting in an intermediate 2 ([TMPH](+)[HC(═O)OB(C6F5)3)](-)), with CO2 being inserted into the B-H bond of 1. However, unlike CO2 insertion into transition-metal hydrides, the direct insertion of CO2 into the B-H bond of 1 is inoperative. The computed CO2 activation mechanism agrees with the experimental synthesis of 2 via reacting HCOOH with TMP/B(C6F5)3. Subsequent to the CO2 activation and B(C6F5)3-mediated hydrosilylation of 2 to regenerate the catalyst (1), giving HC(═O)OSiEt3 (5), three hydride-transfer steps take place, sequentially transferring H(δ-) of Et3SiH to 5 to (Et3SiO)2CH2 (6, the product of the first hydride-transfer step) to Et3SiOCH3 (7, the product of the second hydride-transfer step) and finally resulting in CH4. These hydride transfers are mediated by B(C6F5)3 via two SN2 processes without involving 1. B(C6F5)3 acts as a hydride carrier that, with the assistance of a nucleophilic attack of 5-7, first grabs H(δ-) from Et3SiH (the first SN2 process), giving HB(C6F5)3(-), and then leave H(δ-) of HB(C6F5)3(-) to the electrophilic C center of 5-7 (the second SN2 process). The SN2 processes utilize the electrophilic and nucleophilic characteristics possessed by the hydride acceptors (5-7). The hydride-transfer mechanism is different from that in the CO2 reduction to methanol catalyzed by N-heterocyclic carbene (NHC) and PCP-pincer nickel hydride ([Ni]H), where the characteristic of possessing a C═O double bond of the hydride acceptors is utilized for hydride transfer. The mechanistic differences elucidate why the present system can completely reduce CO2 to CH4, whereas NHC and [Ni]H catalysts can only mediate the reduction of CO2 to [Si]OCH3 and catBOCH3, respectively. Understanding this could help in the development of catalysts for selective CO2 reduction to CH4 or methanol.

RARE EARTH ELEMENTS: A REVIEW OF PRODUCTION, PROCESSING, RECYCLING, AND ASSOCIATED ENVIRONMENTAL ISSUES

EPA Science Inventory

Rare earth elements (REEs) are a group of 15 chemical elements in the periodic table, specifically the lanthanides. Two other elements, scandium and yttrium, have a similar physiochemistry to the lanthanides, are commonly found in the same mineral assemblages, and are often refe...

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.

Agile Thermal Management STT-RX. Catalytic Influence of Ni-based Additives on the Dehydrogentation Properties of Ball Milled MgH2 (PREPRINT)

DTIC Science & Technology

2011-12-01

Wronski: Particle size, grain size and gamma-MgH2 effects on the desorption properties of nanocrystal- line commercial magnesium hydride processed...Catalytic effects of various forms of nickel on the synthesis rate and hydrogen desorption properties of nanocrystalline magnesium hydride (MgH2...dehydrogenation reaction. 15. SUBJECT TERMS magnesium hydride , MgH, thermal energy storage materials, endothermic reaction 16. SECURITY CLASSIFICATION

Lih thermal energy storage device

DOEpatents

Olszewski, Mitchell; Morris, David G.

1994-01-01

A thermal energy storage device for use in a pulsed power supply to store waste heat produced in a high-power burst operation utilizes lithium hydride as the phase change thermal energy storage material. The device includes an outer container encapsulating the lithium hydride and an inner container supporting a hydrogen sorbing sponge material such as activated carbon. The inner container is in communication with the interior of the outer container to receive hydrogen dissociated from the lithium hydride at elevated temperatures.

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

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.

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.

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.

Making a Splash in Homogeneous CO₂ Hydrogenation: Elucidating the Impact of Solvent on Catalytic Mechanisms.

PubMed

Wiedner, Eric; Linehan, John

2018-06-06

Molecular catalysts for hydrogenation of CO₂ are widely studied as a means of chemical hydrogen storage. Catalysts are traditionally designed from the perspective of controlling the ligands bound to the metal. In recent years, studies have shown that the solvent can also play a key role in the mechanism of CO₂ hydrogenation. A prominent example is the impact of the solvent on the thermodynamic hydride donor ability, or hydricity, of metal hydride complexes relative to the hydride acceptor ability of CO₂. In some cases, simply changing from an organic solvent to water can reverse the direction of hydride transfer between a metal hydride and CO₂. Additionally, the solvent can impact catalysis by converting CO₂ into carbonate species, as well as activate intermediate products for hydrogenation to more reduced products. By understanding the substrate and product speciation, as well as the reactivity of the catalyst towards the substrate, the solvent can be used as a central design component for the rational development of new catalytic systems. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

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.

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.

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.

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.

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.

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

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.

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

Method of forming a chemical composition

DOEpatents

Bingham, Dennis N.; Wilding, Bruce M.; Klingler, Kerry M.; Zollinger, William T.; Wendt, Kraig M.

2007-10-09

A method of forming a chemical composition such as a chemical hydride is described and which includes the steps of selecting a composition having chemical bonds and which is capable of forming a chemical hydride; providing a source of hydrogen; and exposing the selected composition to an amount of ionizing radiation to encourage the changing of the chemical bonds of the selected composition, and chemically reacting the selected composition with the source of hydrogen to facilitate the formation of a chemical hydride.

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.

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.

LiH thermal energy storage device

DOEpatents

Olszewski, M.; Morris, D.G.

1994-06-28

A thermal energy storage device for use in a pulsed power supply to store waste heat produced in a high-power burst operation utilizes lithium hydride as the phase change thermal energy storage material. The device includes an outer container encapsulating the lithium hydride and an inner container supporting a hydrogen sorbing sponge material such as activated carbon. The inner container is in communication with the interior of the outer container to receive hydrogen dissociated from the lithium hydride at elevated temperatures. 5 figures.

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.

METHOD OF PREPARING URANIUM, THORIUM, OR PLUTONIUM OXIDES IN LIQUID BISMUTH

DOEpatents

Davidson, J.K.; Robb, W.L.; Salmon, O.N.

1960-11-22

A method is given for forming compositions, as well as the compositions themselves, employing uranium hydride in a liquid bismuth composition to increase the solubility of uranium, plutonium and thorium oxides in the liquid bismuth. The finely divided oxide of uranium, plutonium. or thorium is mixed with the liquid bismuth and uranium hydride, the hydride being present in an amount equal to about 3 at. %, heated to about 5OO deg C, agitated and thereafter cooled and excess resultant hydrogen removed therefrom.

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 effects of multidimensional phase growth and transitions between rate-limiting processes on the experimentally determined reaction rates. Unlike conventional solid state reaction analysis methods, this model relies fully on rate parameters based on the physical mechanisms occurring in the hydride reaction and can be extended to reactions in any dimension.

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)

10 CFR Appendix L to Part 110 - Illustrative List of Byproduct Materials Under NRC Export/Import Licensing Authority a

Code of Federal Regulations, 2012 CFR

2012-01-01

...) Scandium 48 (Sc 48) Selenium 75 (Se 75) Silicon 31 (Si 31) Silver 105 (Ag 105) Silver 110m (Ag 110m) Silver 111 (Ag 111) Sodium 22 (Na 22) Sodium 24 (Na 24) Strontium 85 (Sr 85) Strontium 89 (Sr 89) Strontium...

10 CFR Appendix L to Part 110 - Illustrative List of Byproduct Materials Under NRC Export/Import Licensing Authority a

Code of Federal Regulations, 2014 CFR

2014-01-01

...) Scandium 48 (Sc 48) Selenium 75 (Se 75) Silicon 31 (Si 31) Silver 105 (Ag 105) Silver 110m (Ag 110m) Silver 111 (Ag 111) Sodium 22 (Na 22) Sodium 24 (Na 24) Strontium 85 (Sr 85) Strontium 89 (Sr 89) Strontium...

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.

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

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

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.

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.

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.

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

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.

Electron spin resonance studies of Bi1-xScxFeO3 nanoparticulates: Observation of an enhanced spin canting over a large temperature range

NASA Astrophysics Data System (ADS)

Titus, S.; Balakumar, S.; Sakar, M.; Das, J.; Srinivasu, V. V.

2017-12-01

Bi1-xScxFeO3 (x = 0.0, 0.1, 0.15, 0.25) nano particles were synthesized by sol gel method. We then probed the spin system in these nano particles using electron spin resonance technique. Our ESR results strongly suggest the scenario of modified spin canted structures. Spin canting parameter Δg/g as a function of temperature for Scandium doped BFO is qualitatively different from undoped BFO. A broad peak is observed for all the Scandium doped BFO samples and an enhanced spin canting over a large temperature range (75-210 K) in the case of x = 0.15 doping. We also showed that the asymmetry parameter and thereby the magneto-crystalline anisotropy in these BSFO nanoparticles show peaks around 230 K for (x = 0.10 and 0.15) and beyond 300 K for x = 0.25 system. Thus, we established that the Sc doping significantly modifies the spin canting and magneto crystalline anisotropy in the BFO system.

Aluminum-Scandium Alloys: Material Characterization, Friction Stir Welding, and Compatibility With Hydrogen Peroxide (MSFC Center Director's Discretionary Fund Final Report, Proj. No. 04-14)

NASA Technical Reports Server (NTRS)

Lee, J. A.; Chen, P. S.

2004-01-01

This Technical Memorandum describes the development of several high-strength aluminum (Al) alloys that are compatible with hydrogen peroxide (H2O2) propellant for NASA Hypersonic-X (Hyper-X) vehicles fuel tanks and structures. The yield strengths for some of these Al-magnesium-based alloys are more than 3 times stronger than the conventional 5254-H112 Al alloy, while maintaining excellent H2O2 compatibility similar to class 1 5254 alloy. The alloy development strategy is to add scandium, zirconium, and other transitional metals with unique electrochemical properties, which will not act as catalysts, to decompose the highly concentrated 90 percent H2O2. Test coupons are machined from sheet metals for H2O2 long-term exposure testing and mechanical properties testing. In addition, the ability to weld the new alloys using friction stir welding has also been explored. The new high-strength alloys could represent an enabling material technology for Hyper-X vehicles, where flight weight reduction is a critical requirement.

Accumulation of radionuclides in bed sediments of the Columbia River between Hanford reactors and McNary Dam

USGS Publications Warehouse

Nelson, Jack L.; Haushild, W.L.

1970-01-01

Amounts of radionuclides from the Hanford reactors contained in bed sediments of the Columbia River were estimated by two methods: (1) from data on radionuclide concentration for the bed sediments between the reactors and McNary Dam, and (2) from data on radionuclide discharge for river stations at Pasco, Washington, and Umatilla, Oregon. Umatilla is 3.2 kilometers below McNary Dam. Accumulations of radionuclides in the Pasco to Umatilla reach estimated by the two methods agree within about 8%. In October 1965 approximately 16,000 curies of gamma emitting radionuclides were resident in bed sediments of the river between the Hanford reactors and McNary Dam. Concentrations and accumulations of chromium-51, zinc-65, cobalt-60, manganese-54, and scandium-46 generally are much higher near McNary Dam than they are in the vicinity of the reactors. These changes are caused by an increase downstream from the reactors in the proportion of the bed sediment that is fine grained and the proportions of the transported zinc, cobalt, manganese, and scandium radionuclides associated with sediment particles.

Stress controlled pulsed direct current co-sputtered Al{sub 1−x}Sc{sub x}N as piezoelectric phase for micromechanical sensor applications

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

Fichtner, Simon, E-mail: sif@tf.uni-kiel.de; Reimer, Tim; Chemnitz, Steffen

2015-11-01

Scandium alloyed aluminum nitride (Al{sub 1−x}Sc{sub x}N) thin films were fabricated by reactive pulsed direct current co-sputtering of separate scandium and aluminum targets with x ≤ 0.37. A significant improvement of the clamped transversal piezoelectric response to strain e{sub 31,f} from −1.28 C/m{sup 2} to −3.01 C/m{sup 2} was recorded, while dielectric constant and loss angle remain low. Further, the built-in stress level of Al{sub 1−x}Sc{sub x}N was found to be tuneable by varying pressure, Ar/N{sub 2} ratio, and Sc content. The thus resulting enhancement of the expectable signal to noise ratio by a factor of 2.1 and the abilitymore » to control built-in stress make the integration of Al{sub 1−x}Sc{sub x}N as the piezoelectric phase of micro-electro-mechanical system sensor applications highly attractive.« less

Optical fluoride sensor based on monomer-dimer equilibrium of scandium(III)-octaethylporphyrin in a plasticized polymeric film.

PubMed

Kang, Youngjea; Kampf, Jeff W; Meyerhoff, Mark E

2007-08-29

A fluoride-selective optical sensor based on scandium(III)-octaethylporphyrin (Sc(III)OEP) as an ionophore within a plasticized PVC film is described. The presence of fluoride ion in the aqueous sample phase increases the formation of a difluoro-bridged Sc(III)OEP dimer species in the polymer film. The ability of the Sc(III) porphyrin to form the dimeric structure in the presence of fluoride is confirmed by UV-vis spectroscopy and X-ray crystallography. For more practical sensing applications, a pH chromoionophore (ETH 7075) is added to the plasticized PVC film along with Sc(III)OEP and the observed optical response is based on coextraction of protons with sample phase fluoride to create the dimeric porphyrin and a protonated chromoionophore species. The selectivity pattern observed is F- > ClO4(-), SCN-, NO3(-) > Br-, Cl-. Only organic salicylate is a significant interferent. Fast and reversible fluoride response is observed over the range of 10(-4) to 10(-2) M fluoride, allowing use of the sensing film in a waveguide configuration for flow-injection measurements.

Optical Fluoride Sensor Based on Monomer-Dimer Equilibrium of Scandium(III)-Octaethylporphyrin in a Plasticized Polymeric Film

PubMed Central

Kang, Youngjea; Kampf, Jeff W.; Meyerhoff, Mark E.

2007-01-01

A fluoride-selective optical sensor based on scandium(III) octaethylporphyrin (Sc(III)OEP) as an ionophore within a plasticized PVC film is described. The presence of fluoride ion in the aqueous sample phase increases the formation of a difluoro-bridged Sc(III)OEP dimer species in the polymer film. The ability of the Sc(III) porphyrin to form the dimeric structure in the presence of fluoride is confirmed by UV-Vis spectroscopy and X-ray crystallography. For more practical sensing applications, a pH chromoionophore (ETH 7075) is added to the plasticized PVC film along with Sc(III)OEP and the observed optical response is based on co-extraction of protons with sample phase fluoride to create the dimeric porphyrin and a protonated chromoionophore species. The selectivity pattern observed is F-≫ClO4-, SCN-, NO3->Br-, Cl-. Only organic salicylate is a significant interferent. Fast and reversible fluoride response is observed over the range of 10-4 ~10-2 M fluoride, allowing use of the sensing film in a waveguide configuration for flow-injection measurements. PMID:17719905

Impact of layer and substrate properties on the surface acoustic wave velocity in scandium doped aluminum nitride based SAW devices on sapphire

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

Gillinger, M., E-mail: manuel.gillinger@tuwien.ac.at; Knobloch, T.; Schneider, M.

2016-06-06

This paper investigates the performance of surface acoustic wave (SAW) devices consisting of reactively sputter deposited scandium doped aluminum nitride (Sc{sub x}Al{sub 1-x}N) thin films as piezoelectric layers on sapphire substrates for wireless sensor or for RF-MEMS applications. To investigate the influence of piezoelectric film thickness on the device properties, samples with thickness ranging from 500 nm up to 3000 nm are fabricated. S{sub 21} measurements and simulations demonstrate that the phase velocity is predominantly influenced by the mass density of the electrode material rather than by the thickness of the piezoelectric film. Additionally, the wave propagation direction is varied by rotatingmore » the interdigital transducer structures with respect to the crystal orientation of the substrate. The phase velocity is about 2.5% higher for a-direction compared to m-direction of the sapphire substrate, which is in excellent agreement with the difference in the anisotropic Young's modulus of the substrate corresponding to these directions.« less

Ratcheting rotation or speedy spinning: EPR and dynamics of Sc3C2@C80.

PubMed

Roukala, Juho; Straka, Michal; Taubert, Stefan; Vaara, Juha; Lantto, Perttu

2017-08-08

Besides their technological applications, endohedral fullerenes provide ideal conditions for investigating molecular dynamics in restricted geometries. A representative of this class of systems, Sc 3 C 2 @C 80 displays complex intramolecular dynamics. The motion of the 45 Sc trimer has a remarkable effect on its electron paramagnetic resonance (EPR) spectrum, which changes from a symmetric 22-peak pattern at high temperature to a single broad lineshape at low temperature. The scandium trimer consists of two equivalent and one inequivalent metal atom, due to the carbon dimer rocking through the Sc 3 triangle. We demonstrate through first-principles molecular dynamics (MD), EPR parameter tensor averaging, and spectral modelling that, at high temperatures, three-dimensional movement of the enclosed Sc 3 C 2 moiety takes place, which renders the metal centers equivalent and their magnetic parameters effectively isotropic. In contrast, at low temperatures the dynamics becomes restricted to two dimensions within the equatorial belt of the I h symmetric C 80 host fullerene. This restores the inequivalence of the scandium centers and causes their anisotropic hyperfine couplings to broaden the experimental spectrum.

Reducing the stochasticity of crystal nucleation to enable subnanosecond memory writing.

PubMed

Rao, Feng; Ding, Keyuan; Zhou, Yuxing; Zheng, Yonghui; Xia, Mengjiao; Lv, Shilong; Song, Zhitang; Feng, Songlin; Ronneberger, Ider; Mazzarello, Riccardo; Zhang, Wei; Ma, Evan

2017-12-15

Operation speed is a key challenge in phase-change random-access memory (PCRAM) technology, especially for achieving subnanosecond high-speed cache memory. Commercialized PCRAM products are limited by the tens of nanoseconds writing speed, originating from the stochastic crystal nucleation during the crystallization of amorphous germanium antimony telluride (Ge 2 Sb 2 Te 5 ). Here, we demonstrate an alloying strategy to speed up the crystallization kinetics. The scandium antimony telluride (Sc 0.2 Sb 2 Te 3 ) compound that we designed allows a writing speed of only 700 picoseconds without preprogramming in a large conventional PCRAM device. This ultrafast crystallization stems from the reduced stochasticity of nucleation through geometrically matched and robust scandium telluride (ScTe) chemical bonds that stabilize crystal precursors in the amorphous state. Controlling nucleation through alloy design paves the way for the development of cache-type PCRAM technology to boost the working efficiency of computing systems. Copyright © 2017 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

Frenolicins C-G, pyranonaphthoquinones from Streptomyces sp. RM-4-15.

PubMed

Wang, Xiachang; Shaaban, Khaled A; Elshahawi, Sherif I; Ponomareva, Larissa V; Sunkara, Manjula; Zhang, Yinan; Copley, Gregory C; Hower, James C; Morris, Andrew J; Kharel, Madan K; Thorson, Jon S

2013-08-23

Appalachian active coal fire sites were selected for the isolation of bacterial strains belonging to the class actinobacteria. A comparison of high-resolution electrospray ionization mass spectrometry (HRESIMS) and ultraviolet (UV) absorption profiles from isolate extracts to natural product databases suggested Streptomyces sp. RM-4-15 to produce unique metabolites. Four new pyranonaphthoquinones, frenolicins C-F (1-4), along with three known analogues, frenolicin (6), frenolicin B (7), and UCF76-A (8), were isolated from the fermentation of this strain. An additional new analogue, frenolicin G (5), along with two known compounds, deoxyfrenolicin (9) and UCF 13 (10), were isolated from the fermentation supplied with 18 mg/L of scandium chloride, the first example, to the best of our knowledge, wherein scandium chloride supplementation led to the confirmed production of new bacterial secondary metabolites. Structures 1-5 were elucidated on the basis of spectral analysis and chemical modification. While frenolicins are best known for their anticoccidial activity, the current study revealed compounds 6-9 to exhibit moderate cytotoxicity against the human lung carcinoma cell line (A549) and thereby extends the anticancer SAR for this privileged scaffold.

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 to identical conditions and the material responses to thermo-mechanical exposures will be different depending on the materials and systems used. The discussions at the workshop showed several gaps in the standardization of processes and techniques necessary to assess the long term performance of irradiated zirconium alloy cladding during dry storage and transport. The development of, and adherence to, standards to help bridge these gaps will strengthen the technical basis for long term storage and post-storage operations, provide consistency across the nuclear industry, maximize the value of most observations, and enhance the understanding of behavioral differences among alloys. The need for, and potential benefits of, developing the recommended standards are illustrated in the various sections of this report.« less

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

Biomimetics of [NiFe]-Hydrogenase: Nickel- or Iron-Centered Proton Reduction Catalysis?

PubMed

Tang, Hao; Hall, Michael B

2017-12-13

The [NiFe] hydrogenase (H2ase) has been characterized in the Ni-R state with a hydride bridging between Fe and Ni but displaced toward the Ni. In nearly all of the synthetic Ni-R models reported so far, the hydride ligand is either displaced toward Fe, or terminally bound to Fe. Recently, a structural and functional [NiFe]-H2ase mimic ( Nat. Chem. 2016 , 8 , 1054 - 1060 ) was reported to produce H 2 catalytically via EECC mechanism through a Ni-centered hydride intermediate like the enzyme. Here, a comprehensive DFT study shows a much lower energy route via an E[ECEC] mechanism through an Fe-centered hydride intermediate. Although catalytic H 2 production occurs at the potential corresponding to the complex's second reduction, a third electron is needed to induce the second proton addition from the weak acid. The first two-electron reductions and a proton addition produce a semibridging hydride with a short Fe-H bond like other structured [NiFe]-biomimetics, but this species is not basic enough to add another proton from the weak acid without the third electron. The calculated mechanism provides insight into the origin of this structure in the enzyme.

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

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.

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

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.

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.

Proceedings 43rd Stanford Geothermal Workshop

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

Simmons, Stuart; Kirby, Stefan; Verplanck, Philip

Herein we summarize the results of an investigation dealing with the concentrations and inventories of strategic, critical and valuable materials (SCVM) in produced fluids from geothermal and hydrocarbon reservoirs (50-250° C) in Nevada and Utah. Water samples were collected from thirty-four production wells across eight geothermal fields, the Uinta Basin oil/gas province in northeast Utah, and the Covenant oil field in southwestern Utah; additional water samples were collected from six hot springs in the Sevier Thermal Belt in southwestern Utah. Most SCVM concentrations in produced waters range from <0.1 to 100 µg/kg; the main exception is lithium, which has concentrationsmore » that range from <1000 to 25,000 ug/kg. Relatively high concentrations of gallium, germanium, scandium, selenium, and tellurium are measured too. Geothermal waters contain very low concentrations of REEs, below analytical detections limits (0.01 µg/kg), but the concentrations of lanthanum, cerium, and europium range from 0.05 to 5 µg/kg in Uinta basin waters. Among the geothermal fields, the Roosevelt Hot Spring reservoir appears to have the largest inventories of germanium and lithium, and Patua appears to have the largest inventories of gallium, scandium, selenium, and tellurium. By comparison, the Uinta basin has larger inventories of gallium. The concentrations of gallium, germanium, lithium, scandium, selenium, and tellurium in produced waters appear to be partly related to reservoir temperature and concentrations of total dissolved salts. The relatively high concentration and large inventory of lithium occurring at Roosevelt Hot Springs may be related to granitic-gneissic crystalline rocks, which host the reservoir. Analyses of calcite scales from Dixie Valley indicate enrichments in cobalt, gallium, gold, palladium, selenium and tellurium, and these metals appear to be depositing at deep levels in production wells due to boiling. Comparisons with SCVM mineral deposits suggest that brines in sedimentary basins, or derived from lacustrine evaporites, enable aqueous transport of gallium, germanium, and lithium.« less

Lewis Acid-Induced Change from Four- to Two-Electron Reduction of Dioxygen Catalyzed by Copper Complexes Using Scandium Triflate

PubMed Central

Kakuda, Saya; Rolle, Clarence; Ohkubo, Kei; Siegler, Maxime A.; Karlin, Kenneth D.; Fukuzumi, Shunichi

2015-01-01

Mononuclear copper complexes, [(tmpa)CuII(CH3CN)](ClO4)2 (1, tmpa = tris(2-pyridylmethyl)amine) and [(BzQ)CuII(H2O)2](ClO4)2 (2, BzQ = bis(2-quinolinylmethyl)benzylamine)], act as efficient catalysts for the selective two-electron reduction of O2 by ferrocene derivatives in the presence of scandium triflate (Sc(OTf)3), in acetone, whereas 1 catalyzes the four-electron reduction of O2 by the same reductant in the presence of Brønsted acids such as triflic acid. Following formation of the peroxo-bridged dicopper(II) complex [(tmpa)CuII(O2)CuII(tmpa)]2+, the two-electron reduced product of O2 with Sc3+ is observed to be scandium peroxide ([Sc3+(O22−)]+). In the presence of three equiv of hexamethylphosphoric triamide (HMPA), [Sc3+(O22−)]+ was oxidized by [Fe(bpy)3]3+ (bpy = 2,2′-bipyridine) to the known superoxide species [(HMPA)3Sc3+(O2•−)]2+ as detected by EPR spectroscopy. A kinetic study revealed that the rate-determining step of the catalytic cycle for the two-electron reduction of O2 with 1 is electron transfer from Fc* to 1 to give a cuprous complex which is highly reactive toward O2, whereas the rate-determining step with 2 is changed to the reaction of the cuprous complex with O2 following electron transfer from ferrocene derivatives to 2. The explanation for the change in catalytic O2-reaction stoichiometry from four-electron with Brønsted acids to two-electron reduction in the presence of Sc3+ and also for the change in the rate-determining step is clarified based on a kinetics interrogation of the overall catalytic cycle as well as each step of the catalytic cycle with study of the observed effects of Sc3+ on copper-oxygen intermediates. PMID:25659416

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.

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

Degtyarenko, N. N.; Mazur, E. A., E-mail: eugen-mazur@mail.ru

The structural, electronic, phonon, and other characteristics of the normal phases of phosphorus hydrides with stoichiometry PH{sub k} are analyzed. The properties of the initial substance, namely, diphosphine are calculated. In contrast to phosphorus hydrides with stoichiometry PH{sub 3}, a quasi-two-dimensional phosphorus-stabilized lattice of metallic hydrogen can be formed in this substance during hydrostatic compression at a high pressure. The formed structure with H–P–H elements is shown to be locally stable in phonon spectrum, i.e., to be metastable. The properties of diphosphine are compared with the properties of similar structures of sulfur hydrides.

Energy Distributions of Neutrons Scattered from Graphite, Light and Heavy Water, Ice, Zirconium Hydride, Lithium Hydride, Sodium Hydride and Ammonium Chloride by the Beryllium Detector Method

DOE R&D Accomplishments Database

Woods, A. D. B.; Brockhouse, Bertram N.; Sakamoto, M.; Sinclair, R. N.

1960-09-12

Energy distributions of neutrons scattered from various moderators and from several hydrogenous substances were measured at energy transfers of 0.02 to 0.24 ev. Results from experiments on graphite, light and heavy water, ice, ZrH, LiH, NaH, and NH4Cl are included. It is noted that the results are of a preliminary character; however, they are probably the most accurate measurements of high-energy transfers yet made. (J.R.D.)

Hydride Conformers of the Nitrogenase FeMo-cofactor Two-Electron Reduced State E2(2H), Assigned Using Cryogenic Intra Electron Paramagnetic Resonance Cavity Photolysis.

PubMed

Lukoyanov, Dmitriy A; Khadka, Nimesh; Yang, Zhi-Yong; Dean, Dennis R; Seefeldt, Lance C; Hoffman, Brian M

2018-03-24

Early studies in which nitrogenase was freeze-trapped during enzymatic turnover revealed the presence of high-spin ( S = 3 / 2 ) electron paramagnetic resonance (EPR) signals from the active-site FeMo-cofactor (FeMo-co) in electron-reduced intermediates of the MoFe protein. Historically denoted as 1b and 1c, each of the signals is describable as a fictitious spin system, S' = 1 / 2 , with anisotropic g' tensor, 1b with g' = [4.21, 3.76, ?] and 1c with g' = [4.69, ∼3.20, ?]. A clear discrepancy between the magnetic properties of 1b and 1c and the kinetic analysis of their appearance during pre-steady-state turnover left their identities in doubt, however. We subsequently associated 1b with the state having accumulated 2[e - /H + ], denoted as E 2 (2H), and suggested that the reducing equivalents are stored on the catalytic FeMo-co cluster as an iron hydride, likely an [Fe-H-Fe] hydride bridge. Intra-EPR cavity photolysis (450 nm; temperature-independent from 4 to 12 K) of the E 2 (2H)/1b state now corroborates the identification of this state as storing two reducing equivalents as a hydride. Photolysis converts E 2 (2H)/1b to a state with the same EPR spectrum, and thus the same cofactor structure as pre-steady-state turnover 1c, but with a different active-site environment. Upon annealing of the photogenerated state at temperature T = 145 K, it relaxes back to E 2 (2H)/1b. This implies that the 1c signal comes from an E 2 (2H) hydride isomer of E 2 (2H)/1b that stores its two reducing equivalents either as a hydride bridge between a different pair of iron atoms or an Fe-H terminal hydride.

Quantification of Lewis acid induced Brønsted acidity of protogenic Lewis bases.

PubMed

Lathem, A Paige; Heiden, Zachariah M

2017-05-09

Proton transfer promoted by the coordination of protogenic Lewis bases to a Lewis acid is a critical step in catalytic transformations. Although the acidification of water upon coordination to a Lewis acid has been known for decades, no attempts have been made to correlate the Brønsted acidity of the coordinated water molecule with Lewis acid strength. To probe this effect, the pK a 's (estimated error of 1.3 pK a units) in acetonitrile of ten protogenic Lewis bases coordinated to seven Lewis acids containing Lewis acidities varying 70 kcal mol -1 , were computed. To quantify Lewis acid strength, the ability to transfer a hydride (hydride donor ability) from the respective main group hydride was used. Coordination of a Lewis acid to water increased the acidity of the bound water molecule between 20 and 50 pK a units. A linear correlation exhibiting a 2.6 pK a unit change of the Lewis acid-water adduct per ten kcal mol -1 change in hydride donor ability of the respective main group hydride was obtained. For the ten protogenic Lewis bases studied, the coordinated protogenic Lewis bases were acidified between 10 and 50 pK a units. On average, a ten kcal mol -1 change in hydride donor ability of the respective main group hydride resulted in about a 2.8 pK a unit change in the Brønsted acidity of the Lewis acid-Lewis base adducts. Since attempts to computationally investigate the pK a of main group dihydrogen complexes were unsuccessful, experimental determination of the first reported pK a of a main group dihydrogen complex is described. The pK a of H 2 -B(C 6 F 5 ) 3 was determined to be 5.8 ± 0.2 in acetonitrile.

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.

Pressure-induced effects and phase relations in Mg2NiH4

NASA Astrophysics Data System (ADS)

Gavra, Z.; Kimmel, G.; Gefen, Y.; Mintz, Moshe H.

1985-05-01

The low-temperature (<210 °C) crystallographic structure, electrical conductivity, and thermal stability of Mg2NiH4 powders compacted under isostatic pressures of up to 10 kbar were studied. A comparison is made with the corresponding properties of the noncompressed material. It has been concluded that under stress-free hydriding conditions performed below 210 °C, a two-phase hydride mixture is formed. Each of the hydride particles consists of an inner core composed of an hydrogen-deficient monoclinic phase coated by a layer of a stoichiometric orthorhombic phase. The monoclinic phase has a metalliclike electrical conductivity while the orthorhombic phase is insulating. High compaction pressures cause the transformation of the orthorhombic structure into the monoclinic one, thereby resulting in a pressure-induced insulator-to-conductor transition. Reduced decomposition temperatures are obtained for the compressed hydrides. This reduction is attributed to kinetic factors rather than to a reduced thermodynamic stability.

The potential pyrophoricity of BMI-SPEC and aluminum plate spent fuels retrieved from underwater storage

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

Ebner, M.A.

1996-08-01

Physical/chemical factors in U metal and hydride combustion, particularly pyrophoricity in ambient environment, were evaluated for BMI-SPEC and UAl{sub x} plate fuels. Some metal fuels may be highly reactive (spontaneously igniting in air) due to high specific surface area, high decay heat, or a high U hydride content from corrosion during underwater storage. However, for the BMI-SPEC and the aluminum plate fuels, this reactivity is too low to present a realistic threat of uncontrolled spontaneous combustion at ambient conditions. While residual U hydride is expected in these corroded fuels, the hydride levels are expected to be too low and themore » configuration too unfavorable to ignite the fuel meat when the fuels are retrieved from the basin and dried. Furthermore the composition and microstructure of the UAl{sub x} fuels further mitigate that risk.« less

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

Reversible hydrogen storage materials

DOEpatents

Ritter, James A [Lexington, SC; Wang, Tao [Columbia, SC; Ebner, Armin D [Lexington, SC; Holland, Charles E [Cayce, SC

2012-04-10

In accordance with the present disclosure, a process for synthesis of a complex hydride material for hydrogen storage is provided. The process includes mixing a borohydride with at least one additive agent and at least one catalyst and heating the mixture at a temperature of less than about 600.degree. C. and a pressure of H.sub.2 gas to form a complex hydride material. The complex hydride material comprises MAl.sub.xB.sub.yH.sub.z, wherein M is an alkali metal or group IIA metal, Al is the element aluminum, x is any number from 0 to 1, B is the element boron, y is a number from 0 to 13, and z is a number from 4 to 57 with the additive agent and catalyst still being present. The complex hydride material is capable of cyclic dehydrogenation and rehydrogenation and has a hydrogen capacity of at least about 4 weight percent.

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.

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

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

(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.

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

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

Chemical reactivity testing for the National Spent Nuclear Fuel Program. Revision 2

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

Koester, L.W.

This quality assurance project plan (QAPjP) summarizes requirements used by Lockheed Martin Energy Systems, Incorporated (LMES) Development Division at Y-12 for conducting chemical reactivity testing of Department of Energy (DOE) owned spent nuclear fuel, sponsored by the National Spent Nuclear Fuel Program (NSNFP). The requirements are based on the NSNFP Statement of work PRO-007 (Statement of Work for Laboratory Determination of Uranium Hydride Oxidation Reaction Kinetics.) This QAPjP will utilize the quality assurance program at Y-12, Y60-101PD, Quality Program Description, and existing implementing procedures for the most part in meeting the NSNFP Statement of Work PRO-007 requirements, exceptions will bemore » noted. The project consists of conducting three separate series of related experiments, ''Passivation of Uranium Hydride Powder With Oxygen and Water'', '''Passivation of Uranium Hydride Powder with Surface Characterization'', and ''Electrochemical Measure of Uranium Hydride Corrosion Rate''.« less

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.

Ti(Ni,Cu) pseudobinary compounds as efficient negative electrodes for Ni-MH batteries

NASA Astrophysics Data System (ADS)

Emami, Hoda; Cuevas, Fermin; Latroche, Michel

2014-11-01

The effect of Ni by Cu substitution on the structural, solid-gas and electrochemical hydrogenation properties of TiNi has been investigated. Pseudo-binary TiNi1-xCux (x ≤ 0.5) compounds have been synthesized by induction melting. They crystallize in B2 structure above 350 K and either in B19‧ (x < 0.1) or B19 (0.2 ≤ x ≤ 0.5) at room temperature (RT). For all compounds, Pressure-Composition Isotherms at 423 K exhibit a single slopping plateau pressure within the range 10-3-1 MPa of hydrogen pressure revealing a metal to hydride transformation. Both the hydrogenation capacity and the hydride stability decrease with Cu-content. The hydrided pseudobinary compounds crystallize in the tetragonal S.G. I4/mmm structure as for TiNi hydride. The electrochemical discharge capacity increases with Cu content from 150 mAh g-1 for TiNi up to 300 mAh g-1 for TiNi0.8Cu0.2 and then decreases again for larger Cu amounts. Electrochemical isotherms and in-situ neutron diffraction measurements at RT demonstrate that such a capacity increase results from a metal to hydride phase transformation in which the hydride phase is destabilized by Cu substitution. The TiNi0.8Cu0.2 compound exhibits interesting cycling stability for 30 cycles and good high-rate capability at D/2 rate. This compound has promising electrochemical properties as compared to commercial LaNi5-type alloys with the advantage of being rare-earth metal free.

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 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.

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)

Storing and transporting energy

DOEpatents

McClaine, Andrew W.; Brown, Kenneth

2010-09-07

Among other things, hydrogen is released from water at a first location using energy from a first energy source; the released hydrogen is stored in a metal hydride slurry; and the metal hydride slurry is transported to a second location remote from the first location.

40 CFR Appendix V to Part 265 - Examples of Potentially Incompatible Waste

Code of Federal Regulations, 2013 CFR

2013-07-01

... Calcium Lithium Magnesium Potassium Sodium Zinc powder Other reactive metals and metal hydrides Potential... concentrated waste in Groups 1-A or 1-B Water Calcium Lithium Metal hydrides Potassium SO2Cl2, SOCl2, PCl3...

40 CFR Appendix V to Part 265 - Examples of Potentially Incompatible Waste

Code of Federal Regulations, 2012 CFR

2012-07-01

... Calcium Lithium Magnesium Potassium Sodium Zinc powder Other reactive metals and metal hydrides Potential... concentrated waste in Groups 1-A or 1-B Water Calcium Lithium Metal hydrides Potassium SO2Cl2, SOCl2, PCl3...

40 CFR Appendix V to Part 265 - Examples of Potentially Incompatible Waste

Code of Federal Regulations, 2014 CFR

2014-07-01

... Calcium Lithium Magnesium Potassium Sodium Zinc powder Other reactive metals and metal hydrides Potential... concentrated waste in Groups 1-A or 1-B Water Calcium Lithium Metal hydrides Potassium SO2Cl2, SOCl2, PCl3...

Method and apparatus for regenerating cold traps within liquid-metal systems

DOEpatents

McKee, Jr., John M.

1976-01-01

Oxide and hydride impurities of a liquid metal such as sodium are removed from a cold trap by heating to a temperature at which the metal hydroxide is stable in a molten state. The partial pressure of hydrogen within the system is measured to determine if excess hydride or oxide is present. Excess hydride is removed by venting hydrogen gas while excess oxide can be converted to molten hydroxide through the addition of hydrogen. The resulting, molten hydroxide is drained from the trap which is then returned to service at cold trap temperatures within the liquid-metal system.

Shield materials recommended for space power nuclear reactors

NASA Technical Reports Server (NTRS)

Kaszubinski, L. J.

1973-01-01

Lithium hydride is recommended for neutron attenuation and depleted uranium is recommended for gamma ray attenuation. For minimum shield weights these materials must be arranged in alternate layers to attenuate the secondary gamma rays efficiently. In the regions of the shield near the reactor, where excessive fissioning occurs in the uranium, a tungsten alloy is used instead. Alloys of uranium such as either the U-0.5Ti or U-8Mo are available to accommodate structural requirements. The zone-cooled casting process is recommended for lithium hydride fabrication. Internal honeycomb reinforcement to control cracks in the lithium hydride is recommended.

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.

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.

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

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.

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

The Role of Large-Scale Motions in Catalysis by Dihydrofolate Reductase

PubMed Central

2011-01-01

Dihydrofolate reductase has long been used as a model system to study the coupling of protein motions to enzymatic hydride transfer. By studying environmental effects on hydride transfer in dihydrofolate reductase (DHFR) from the cold-adapted bacterium Moritella profunda (MpDHFR) and comparing the flexibility of this enzyme to that of DHFR from Escherichia coli (EcDHFR), we demonstrate that factors that affect large-scale (i.e., long-range, but not necessarily large amplitude) protein motions have no effect on the kinetic isotope effect on hydride transfer or its temperature dependence, although the rates of the catalyzed reaction are affected. Hydrogen/deuterium exchange studies by NMR-spectroscopy show that MpDHFR is a more flexible enzyme than EcDHFR. NMR experiments with EcDHFR in the presence of cosolvents suggest differences in the conformational ensemble of the enzyme. The fact that enzymes from different environmental niches and with different flexibilities display the same behavior of the kinetic isotope effect on hydride transfer strongly suggests that, while protein motions are important to generate the reaction ready conformation, an optimal conformation with the correct electrostatics and geometry for the reaction to occur, they do not influence the nature of the chemical step itself; large-scale motions do not couple directly to hydride transfer proper in DHFR. PMID:22060818

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.

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.

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

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.

DECONTAMINATION OF URANIUM

DOEpatents

Spedding, F.H.; Butler, T.A.

1962-05-15

A process is given for separating fission products from uranium by extracting the former into molten aluminum. Phase isolation can be accomplished by selectively hydriding the uranium at between 200 and 300 deg C and separating the hydride powder from coarse particles of fissionproduct-containing aluminum. (AEC)

Method for producing electrodes using microscale or nanoscale materials obtained from hydrogendriven metallurgical reactions

DOEpatents

Reilly, James J.; Adzic, Gordana D.; Johnson, John R.; Vogt, Thomas; McBreen, James

2003-09-02

A method is provided for producing electrodes using microscale and nanoscale metal materials formed from hydrogen driven metallurgical processes; such a the HD (hydriding, dehydriding) process, the HDDR (hydriding, dehydriding, disproportionation, and recombination) process, and variants thereof.

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 tested under simulated usage and accident conditions. Mitigating the hazards associated with reactive metal hydrides during an accident while finding a way to keep the original capability of the active material intact during normal use has been the focus of this work. These composites were made by polymerizing vinyl monomers using free-radical polymerization chemistry, in the presence of the metal hydride, in this case a prepared sodium alanate (chosen as a representative reactive metal hydride). It was found that the polymerization of styrene and divinyl benzene could be initiated using AIBN in toluene at 70°C. The resulting composite materials can be either hard or brittle solids depending on the cross-linking density. Thermal decomposition of these styrene-based composite materials is lower than neat polystyrene indicating that the chemical nature of the polymer is affected by the formation of the composite. The char-forming nature of cross-linked polystyrene is low and therefore, not an ideal polymer for hazard mitigation. To obtain composite materials containing a polymer with higher char-forming potential, siloxane-based monomers were investigated. Four vinyl-containing siloxane oligomers were polymerized with and without added styrene and divinyl benzene. Like the styrene materials, these composite materials exhibited thermal decomposition behavior significantly different than the neat polymers. Specifically, the thermal decomposition temperature was shifted approximately 100 °C lower than the neat polymer signifying a major chemical change to the polymer network. Thermal analysis of the cycled samples was performed on the siloxane-based composite materials. It was found that after 30 cycles the siloxane-containing polymer composite material has similar TGA/DSC-MS traces as the virgin composite material indicating that the polymer is physically intact upon cycling. Hydrogen capacity measurements revealed that addition of the polymer to the metal hydride in the form of a composite material reduced the inherent hydrogen storage capacity of the material. This reduction in capacity was observed to be independent of the amount of charge/discharge cycles except for the composites containing siloxane, which showed less of an impact on hydrogen storage capacity as it was cycled further. While the reason for this is not clear, it may be due to a chemically stabilizing effect of the siloxane on the metal hydride. Flow-through calorimetry was used to characterize the mitigating effectiveness of the different composites relative to the neat (no polymer) material. The composites were found to be initially effective at reducing the amount of heat released during oxidation, and the best performing material was the siloxane-containing composite which reduced the heat release to less than 50% of the value of the neat material. However, upon cycling the composites, all mitigating behavior was lost. The combined results of the flow-through calorimetry, hydrogen capacity, and thermogravimetric analysis tests lead to the proposed conclusion that while the polymer composites have mitigating potential and are physically robust under cycling, they undergo a chemical change upon cycling that makes them ineffective at mitigating heat release upon oxidation of the metal hydride.« less

Nondestructive hydrogen analysis of steam-oxidized Zircaloy-4 by wide-angle neutron scattering

NASA Astrophysics Data System (ADS)

Yan, Yong; Qian, Shuo; Garrison, Ben; Smith, Tyler; Kim, Peter

2018-04-01

A nondestructive neutron scattering method to precisely measure the hydrogen content in high-temperature steam-oxidized Zircaloy-4 cladding was developed. Zircaloy-4 cladding was used to produce hydrided specimens with hydrogen content up to ≈500 wppm. Following hydrogen charging, the hydrogen content of the hydrided specimens was measured using the vacuum hot extraction method, by which the samples with desired hydrogen concentrations were selected for the neutron study. The hydrided samples were then oxidized in steam up to ≈6.0 wt. % at 1100 °C. Optical microscopy shows that our hydriding procedure results in uniform distribution of circumferential hydrides across the wall thickness, and uniform oxide layers were formed on the sample surfaces by the steam oxidation. Small- and wide-angle neutron scattering were simultaneously performed to provide a quick (less than an hour per sample) measurement of the hydrogen content in various types of hydrided and oxidized Zircaloy-4. Our study demonstrates that the hydrogen in pre-oxidized Zircaloy-4 cladding can be measured very accurately by both small- and wide-angle neutron scattering. For steam-oxidized samples, the small-angle neutron scattering is contaminated with coherent scattering from additional structural features induced by the steam oxidation. However, the scattering intensity of the wide-angle neutron scattering increases proportionally with the hydrogen charged in the samples. The hydrogen content and wide-angle neutron scattering intensity are highly linearly correlated for the oxidized cladding samples examined in this work, and can be used to precisely determine the hydrogen content in steam-oxidized Zircaloy-4 samples. Hydrogen contents determined by neutron scattering of oxidation samples were also found to be consistent with the results of chemical analysis within acceptable margins for error.

Investigation of Y6Mn23 and YMn12 intermetallic alloys under high hydrogen pressure

NASA Astrophysics Data System (ADS)

Filipek, S. M.; Sato, R.; Kuriyama, N.; Tanaka, H.; Takeichi, N.

2010-03-01

Among three intermetallic compounds existing in Y-Mn system the YMn2 and Y6Mn23 can easily form interstitial hydrides while for YMn12 existence of hydride has never been reported. At moderate hydrogen pressure YMn2 and Y6Mn23 transform into YMn2H4.5 and Y6Mn23H25 respectively. At high hydrogen pressure the YMn2 (C15 or C14 parent structure) forms a unique YMn2H6 (s.g. Fm3m) complex hydride of fluorite structure in which one Mn atom Mn(1) and Y randomly occupy the 8c sites while second manganese (Mn2) in position 4a forms complex anion with 6 hydrogen atoms located in positions 24e. Formation of YMn2H6 independently of the structure of parent phase (C14 or C15) as well as occupation of the same site (8c) by Y and Mn(1) atoms suggested that also Y6Mn23 and YMn12 could transform into YMn2H6 - type hydride in which suitable number of Y atoms will be substituted by Mn(1) in the 8c positions. This assumption was confirmed by exposing R6Mn23 and RMn12 to 1 GPa of hydrogen pressure at 1000C. Formation of (RxMn2-x)MnH6 (where x = 18/29 or 3/13 for R6Mn23 and RMn12 hydrides respectively) was confirmed by XRD. Hydrogen concentration in both R6Mn23 and RMn12 based hydrides reached H/Me = 2 thus value two times higher than in R6Mn23H25.

Nondestructive hydrogen analysis of steam-oxidized Zircaloy-4 by wide-angle neutron scattering

DOE PAGES

Yan, Yong; Qian, Shuo; Garrison, Ben; ...

2018-04-15

In this study, a nondestructive neutron scattering method to precisely measure the hydrogen content in high-temperature steam-oxidized Zircaloy-4 cladding was developed. Zircaloy-4 cladding was used to produce hydrided specimens with hydrogen content up to ≈500 wppm. Following hydrogen charging, the hydrogen content of the hydrided specimens was measured using the vacuum hot extraction method, by which the samples with desired hydrogen concentrations were selected for the neutron study. The hydrided samples were then oxidized in steam up to ≈6.0wt. % at 1100°C. Optical microscopy shows that our hydriding procedure results in uniform distribution of circumferential hydrides across the wall thickness,more » and uniform oxide layers were formed on the sample surfaces by the steam oxidation. Small- and wide-angle neutron scattering were simultaneously performed to provide a quick (less than an hour per sample) measurement of the hydrogen content in various types of hydrided and oxidized Zircaloy-4. Our study demonstrates that the hydrogen in pre-oxidized Zircaloy-4 cladding can be measured very accurately by both small- and wide-angle neutron scattering. For steam-oxidized samples, the small-angle neutron scattering is contaminated with coherent scattering from additional structural features induced by the steam oxidation. However, the scattering intensity of the wide-angle neutron scattering increases proportionally with the hydrogen charged in the samples. The hydrogen content and wide-angle neutron scattering intensity are highly linearly correlated for the oxidized cladding samples examined in this work, and can be used to precisely determine the hydrogen content in steam-oxidized Zircaloy-4 samples. Hydrogen contents determined by neutron scattering of oxidation samples were also found to be consistent with the results of chemical analysis within acceptable margins for error.« less

Nondestructive hydrogen analysis of steam-oxidized Zircaloy-4 by wide-angle neutron scattering

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

Yan, Yong; Qian, Shuo; Garrison, Ben

In this study, a nondestructive neutron scattering method to precisely measure the hydrogen content in high-temperature steam-oxidized Zircaloy-4 cladding was developed. Zircaloy-4 cladding was used to produce hydrided specimens with hydrogen content up to ≈500 wppm. Following hydrogen charging, the hydrogen content of the hydrided specimens was measured using the vacuum hot extraction method, by which the samples with desired hydrogen concentrations were selected for the neutron study. The hydrided samples were then oxidized in steam up to ≈6.0wt. % at 1100°C. Optical microscopy shows that our hydriding procedure results in uniform distribution of circumferential hydrides across the wall thickness,more » and uniform oxide layers were formed on the sample surfaces by the steam oxidation. Small- and wide-angle neutron scattering were simultaneously performed to provide a quick (less than an hour per sample) measurement of the hydrogen content in various types of hydrided and oxidized Zircaloy-4. Our study demonstrates that the hydrogen in pre-oxidized Zircaloy-4 cladding can be measured very accurately by both small- and wide-angle neutron scattering. For steam-oxidized samples, the small-angle neutron scattering is contaminated with coherent scattering from additional structural features induced by the steam oxidation. However, the scattering intensity of the wide-angle neutron scattering increases proportionally with the hydrogen charged in the samples. The hydrogen content and wide-angle neutron scattering intensity are highly linearly correlated for the oxidized cladding samples examined in this work, and can be used to precisely determine the hydrogen content in steam-oxidized Zircaloy-4 samples. Hydrogen contents determined by neutron scattering of oxidation samples were also found to be consistent with the results of chemical analysis within acceptable margins for error.« less

PLUTONIUM-HYDROGEN REACTION PRODUCT, METHOD OF PREPARING SAME AND PLUTONIUM POWDER THEREFROM

DOEpatents

Fried, S.; Baumbach, H.L.

1959-12-01

A process is described for forming plutonlum hydride powder by reacting hydrogen with massive plutonium metal at room temperature and the product obtained. The plutonium hydride powder can be converted to plutonium powder by heating to above 200 deg C.

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.

Mixed quantum-classical simulation of the hydride transfer reaction catalyzed by dihydrofolate reductase based on a mapped system-harmonic bath model

NASA Astrophysics Data System (ADS)

Xu, Yang; Song, Kai; Shi, Qiang

2018-03-01

The hydride transfer reaction catalyzed by dihydrofolate reductase is studied using a recently developed mixed quantum-classical method to investigate the nuclear quantum effects on the reaction. Molecular dynamics simulation is first performed based on a two-state empirical valence bond potential to map the atomistic model to an effective double-well potential coupled to a harmonic bath. In the mixed quantum-classical simulation, the hydride degree of freedom is quantized, and the effective harmonic oscillator modes are treated classically. It is shown that the hydride transfer reaction rate using the mapped effective double-well/harmonic-bath model is dominated by the contribution from the ground vibrational state. Further comparison with the adiabatic reaction rate constant based on the Kramers theory confirms that the reaction is primarily vibrationally adiabatic, which agrees well with the high transmission coefficients found in previous theoretical studies. The calculated kinetic isotope effect is also consistent with the experimental and recent theoretical results.

Prediction of the electronic structures, thermodynamic and mechanical properties in manganese doped magnesium-based alloys and their saturated hydrides based on density functional theory

NASA Astrophysics Data System (ADS)

Zhang, Ziying; Zhang, Huizhen; Zhao, Hui; Yu, Zhishui; He, Liang; Li, Jin

2015-04-01

The crystal structures, electronic structures, thermodynamic and mechanical properties of Mg2Ni alloy and its saturated hydride with different Mn-doping contents are investigated using first-principles density functional theory. The lattice parameters for the Mn-doped Mg2Ni alloys and their saturated hydrides decreased with an increasing Mn-doping content because of the smaller atomic size of Mn compared with that of Mg. Analysis of the formation enthalpies and electronic structures reveal that the partial substitution of Mg with Mn reduces the stability of Mg2Ni alloy and its saturated hydride. The calculated elastic constants indicate that, although the partial substitution of Mg with Mn lowers the toughness of the hexagonal Mg2Ni alloy, the charge/discharge cycles are elevated when the Mn-doping content is high enough to form the predicted intermetallic compound Mg3MnNi2.

Superconductivity in Hydrides Doped with Main Group Elements Under Pressure

NASA Astrophysics Data System (ADS)

Shamp, Andrew; Zurek, Eva

2017-01-01

A priori crystal structure prediction techniques have been used to explore the phase diagrams of hydrides of main group elements under pressure. A number of novel phases with the chemical formulas MHn, n > 1 and M = Li, Na, K, Rb, Cs; MHn, n > 2 and M= Mg, Ca, Sr, Ba; HnI with n > 1 and PH, PH2, PH3 have been predicted to be stable at pressures achievable in diamond anvil cells. The hydrogenic lattices within these phases display a number of structural motifs including H2δ- , H-, H-3 , as well as one-dimensional and three-dimensional extended structures. A wide range of superconducting critical temperatures, Tcs, are predicted for these hydrides. The mechanism of metallization and the propensity for superconductivity are dependent upon the structural motifs present in these phases, and in particular on their hydrogenic sublattices. Phases that are thermodynamically unstable, but dynamically stable, are accessible experimentally. The observed trends provide insight on how to design hydrides that are superconducting at high temperatures.

Effect of cathodic polarization on coating doxycycline on titanium surfaces.

PubMed

Geißler, Sebastian; Tiainen, Hanna; Haugen, Håvard J

2016-06-01

Cathodic polarization has been reported to enhance the ability of titanium based implant materials to interact with biomolecules by forming titanium hydride at the outermost surface layer. Although this hydride layer has recently been suggested to allow the immobilization of the broad spectrum antibiotic doxycycline on titanium surfaces, the involvement of hydride in binding the biomolecule onto titanium remains poorly understood. To gain better understanding of the influence this immobilization process has on titanium surfaces, mirror-polished commercially pure titanium surfaces were cathodically polarized in the presence of doxycycline and the modified surfaces were thoroughly characterized using atomic force microscopy, electron microscopy, secondary ion mass spectrometry, and angle-resolved X-ray spectroscopy. We demonstrated that no hydride was created during the polarization process. Doxycycline was found to be attached to an oxide layer that was modified during the electrochemical process. A bacterial assay using bioluminescent Staphylococcus epidermidis Xen43 showed the ability of the coating to reduce bacterial colonization and planktonic bacterial growth. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

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.

Inhibitive effect of Pt on Pd-hydride formation of Pd@Pt core-shell electrocatalysts: An in situ EXAFS and XRD study

DOE PAGES

Wise, Anna M.; Richardson, Peter W.; Price, Stephen W. T.; ...

2017-12-27

In situ EXAFS and XRD have been used to study the electrochemical formation of hydride phases, H abs, in 0.5 M H 2SO 4 for a Pd/C catalyst and a series of Pd@Pt core-shell catalysts with varying Pt shell thickness, from 0.5 to 4 monolayers. Based on the XRD data a 3% lattice expansion is observed for the Pd/C core catalyst upon hydride formation at 0.0 V. In contrast, the expansion was ≤0.6% for all of the core-shell catalysts. The limited extent of the lattice expansion observed suggests that hydride formation, which may occur during periodic active surface area measurementsmore » conducting during accelerated aging tests or driven by H 2 crossover in PEM fuel cells, is unlikely to contribute significantly to the degradation of Pd@Pt core-shell electrocatalysts in contrast to the effects of oxide formation.« less

Inhibitive effect of Pt on Pd-hydride formation of Pd@Pt core-shell electrocatalysts: An in situ EXAFS and XRD study

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

Wise, Anna M.; Richardson, Peter W.; Price, Stephen W. T.

In situ EXAFS and XRD have been used to study the electrochemical formation of hydride phases, H abs, in 0.5 M H 2SO 4 for a Pd/C catalyst and a series of Pd@Pt core-shell catalysts with varying Pt shell thickness, from 0.5 to 4 monolayers. Based on the XRD data a 3% lattice expansion is observed for the Pd/C core catalyst upon hydride formation at 0.0 V. In contrast, the expansion was ≤0.6% for all of the core-shell catalysts. The limited extent of the lattice expansion observed suggests that hydride formation, which may occur during periodic active surface area measurementsmore » conducting during accelerated aging tests or driven by H 2 crossover in PEM fuel cells, is unlikely to contribute significantly to the degradation of Pd@Pt core-shell electrocatalysts in contrast to the effects of oxide formation.« less

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.

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.

Production of scandium-44 m and scandium-44 g with deuterons on calcium-44: cross section measurements and production yield calculations.

PubMed

Duchemin, C; Guertin, A; Haddad, F; Michel, N; Métivier, V

2015-09-07

HIGHLIGHTS • Production of Sc-44 m, Sc-44 g and contaminants. • Experimental values determined using the stacked-foil technique. • Thick-Target production Yield (TTY) calculations. • Comparison with the TALYS code version 1.6.Among the large number of radionuclides of medical interest, Sc-44 is promising for PET imaging. Either the ground-state Sc-44 g or the metastable-state Sc-44 m can be used for such applications, depending on the molecule used as vector. This study compares the production rates of both Sc-44 states, when protons or deuterons are used as projectiles on an enriched Calcium-44 target. This work presents the first set of data for the deuteron route. The results are compared with the TALYS code. The Thick-Target production Yields of Sc-44 m and Sc-44 g are calculated and compared with those for the proton route for three different scenarios: the production of Sc-44 g for conventional PET imaging, its production for the new 3 γ imaging technique developed at the SUBATECH laboratory and the production of a Sc-44 m/Sc-44 g in vivo generator for antibody labelling.

Evaluation of stability region for scandium-containing rare-earth garnet single crystals and their congruent-melting compositions

NASA Astrophysics Data System (ADS)

Kaurova, I. A.; Domoroshchina, E. N.; Kuz'micheva, G. M.; Rybakov, V. B.

2017-06-01

Single crystals of scandium-containing rare-earth garnets in system R-Sc-C-O (R3+=Y, Gd; C3+=Al, Ga) have been grown by the Czochralski technique. X-ray diffraction analysis has been used to refine crystal compositions. The fundamental difference between the melt compositions and compositions of grown crystals has been found (except for compositions of congruent-melting compounds, CMC). The specific features of garnet solid solution formation have been established and the ternary diagrams with real or hypothetical phases have been built. The dinamics of coordination polyhedra changes with the formation of substitutional solid solutions have been proposed based on the mathematical modeling and experimental data. Possible existence of CMC with garnet structure in different systems as well as limit content of Sc ions in dodecahedral and octahedral sites prior to their partial substitution of ions, located in other sites, have been evaluated. It was established that the redistribution of cations over crystallographic sites (antistructural point defects) due to system self-organization to maintain its stability may be accompanied by cation ordering and the symmetry change of individual polyhedrons and/or the whole crystal.

Near Infrared Laser Spectroscopy of Scandium Monobromide

NASA Astrophysics Data System (ADS)

Xia, Ye; Cheung, A. S.-C.; Liao, Zhenwu; Yang, Mei; Chan, Man-Chor

2012-06-01

High resolution laser spectrum of scandium monobromide (ScBr) between 787 and 845 nm has been investigated using the technique of laser vaporization/reaction with free jet expansion and laser induced fluorescence spectroscopy. ScBr was produced by reacting laser vaporized Sc atoms with ethyl bromide (C2H5Br). Spectra of six vibrational bands of both Sc79Br and Sc81Br isotopomers of the C1 Σ+ - X1 Σ+ transition and seven vibrational bands of the e3 Δ - a3 Δ transition were obtained and analyzed. Least-squares fit of the measured line positions for the singlet transitions yielded accurate molecular constants for the v = 0 - 3 levels of the C1 Σ+ state and the v = 0 - 2 levels of the X1 Σ+ state. Similar least-squares fit for the triplet transitions yielded molecular constants for the v = 0 - 2 levels of both e3 Δ and a3 Δ states. The equilibrium bond length, r_0, of the a3 Δ state has been determined to be 2.4789 Å. Financial support from the Research Grants Council of the Hong Kong Special Administrative Region, China (Project No. HKU 701008P) is gratefully acknowledged

Mutual solubility of scandium oxide-hematite magnetic nanocomposites: Mössbauer spectroscopy investigation

NASA Astrophysics Data System (ADS)

Allwes, Mark; Mekaoui, Mehdi; Sorescu, Monica

2017-08-01

xSc2O3-(1-x)α-Fe2O3 (x = 0.1, 0.3 and 0.5) nanocomposite systems were successfully synthesized by mechanochemical activation of Sc2O3 and α-Fe2O3 mixtures for 0-12 h of ball milling time. Mössbauer investigations were performed to study the structural and magnetic properties of xSc2O3-(1-x)α-Fe2O3 nanoparticle systems during the mechanochemical activation treatment. The Mössbauer studies showed that the spectrum of the mechanochemically activated composites evolved from a sextet for hematite to sextets and a doublet upon duration of the milling process with scandium oxide. Mutual solubility was achieved at the nanoscopic level only. A comprehensive Mössbauer study was performed by recording the recoilless fraction f as function of the ball milling time using our dual absorber method. The results obtained indicate that prolonged ball milling times favor formation of the Fe:Sc2O3 non-magnetic phase and decrease of the grain sizes for both magnetic and non-magnetic components, leading to a maximum in the recoilless fraction followed by its decay.

Green and selective polycondensation methods toward linear sorbitol-based polyesters: enzymatic versus organic and metal-based catalysis.

PubMed

Gustini, Liliana; Lavilla, Cristina; Janssen, William W T J; Martínez de Ilarduya, Antxon; Muñoz-Guerra, Sebastián; Koning, Cor E

2016-08-23

Renewable polyesters derived from a sugar alcohol (i.e., sorbitol) were synthesized by solvent-free polycondensation. The aim was to prepare linear polyesters with pendant hydroxyl groups along the polymer backbone. The performance of the sustainable biocatalyst SPRIN liposorb CALB [an immobilized form of Candida antarctica lipase B (CALB); SPRIN technologies] and the organo-base catalyst 1,5,7-triazabicyclo[4,4,0]dec-5-ene (TBD) were compared with two metal-based catalysts: dibutyl tin oxide (DBTO) and scandium trifluoromethanesulfonate [also known as scandium triflate, Sc(OTf)3 ]. For the four catalytic systems, the efficiency and selectivity for the incorporation of sorbitol were studied, mainly using (13) C and (31) P NMR spectroscopies, whereas side reactions, such as ether formation and dehydration of sorbitol, were evaluated using MALDI-TOF-MS. Especially the biocatalyst SPRIN liposorb CALB succeeded in incorporating sorbitol in a selective way without side reactions, leading to close-to-linear polyesters. By using a renewable hydroxyl-reactive curing agent based on l-lysine, transparent and glossy poly(ester urethane) networks were successfully synthesized offering a tangible example of bio-based coatings. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

Development of Novel Metal Hydride-Carbon Nanomaterial Based Nanocomposites as Anode Electrode Materials for Lithium Ion Battery

DTIC Science & Technology

2014-06-30

The aim of this study is to develop metal hydride-carbon nanomaterial based nanocomposites as anode electrode materials for high capacity lithium ion battery and...henceforth to develop high energy density, and good cyclic stability lithium ion battery .

40 CFR 420.81 - Specialized definitions.

Code of Federal Regulations, 2013 CFR

2013-07-01

...-finished steel products by the action of molten salt baths other than those containing sodium hydride. (b... the action of molten salt baths containing sodium hydride. (c) The term batch, sheet and plate means... STANDARDS IRON AND STEEL MANUFACTURING POINT SOURCE CATEGORY Salt Bath Descaling Subcategory § 420.81...

40 CFR 420.81 - Specialized definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

...-finished steel products by the action of molten salt baths other than those containing sodium hydride. (b... the action of molten salt baths containing sodium hydride. (c) The term batch, sheet and plate means... STANDARDS IRON AND STEEL MANUFACTURING POINT SOURCE CATEGORY Salt Bath Descaling Subcategory § 420.81...

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.

The Synthesis and Organic Chemistry of the Boron-Silicon Bond.

DTIC Science & Technology

1985-12-12

o . ikaline hydrogen peroxide and slowly in air, but was Inert to methanol, water, bromine and tributyltin hydride. In addition it . did not...with methanol, water, bromine or tributyltin hydride. Interestingly 2 did react with organolithium and organomagnesium reagents to give the B-alkyl-9

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

Computation provides chemical insight into the diverse hydride NMR chemical shifts of [Ru(NHC)4(L)H]0/+ species (NHC = N-heterocyclic carbene; L = vacant, H2, N2, CO, MeCN, O2, P4, SO2, H-, F- and Cl-) and their [Ru(R2PCH2CH2PR2)2(L)H]+ congeners.

PubMed

Häller, L Jonas L; Mas-Marzá, Elena; Cybulski, Mateusz K; Sanguramath, Rajashekharayya A; Macgregor, Stuart A; Mahon, Mary F; Raynaud, Christophe; Russell, Christopher A; Whittlesey, Michael K

2017-02-28

Relativistic density functional theory calculations, both with and without the effects of spin-orbit coupling, have been employed to model hydride NMR chemical shifts for a series of [Ru(NHC) 4 (L)H] 0/+ species (NHC = N-heterocyclic carbene; L = vacant, H 2 , N 2 , CO, MeCN, O 2 , P 4 , SO 2 , H - , F - and Cl - ), as well as selected phosphine analogues [Ru(R 2 PCH 2 CH 2 PR 2 ) 2 (L)H] + (R = i Pr, Cy; L = vacant, O 2 ). Inclusion of spin-orbit coupling provides good agreement with the experimental data. For the NHC systems large variations in hydride chemical shift are shown to arise from the paramagnetic term, with high net shielding (L = vacant, Cl - , F - ) being reinforced by the contribution from spin-orbit coupling. Natural chemical shift analysis highlights the major orbital contributions to the paramagnetic term and rationalizes trends via changes in the energies of the occupied Ru d π orbitals and the unoccupied σ* Ru-H orbital. In [Ru(NHC) 4 (η 2 -O 2 )H] + a δ-interaction with the O 2 ligand results in a low-lying LUMO of d π character. As a result this orbital can no longer contribute to the paramagnetic shielding, but instead provides additional deshielding via overlap with the remaining (occupied) d π orbital under the L z angular momentum operator. These two effects account for the unusual hydride chemical shift of +4.8 ppm observed experimentally for this species. Calculations reproduce hydride chemical shift data observed for [Ru( i Pr 2 PCH 2 CH 2 P i Pr 2 ) 2 (η 2 -O 2 )H] + (δ = -6.2 ppm) and [Ru(R 2 PCH 2 CH 2 PR 2 ) 2 H] + (ca. -32 ppm, R = i Pr, Cy). For the latter, the presence of a weak agostic interaction trans to the hydride ligand is significant, as in its absence (R = Me) calculations predict a chemical shift of -41 ppm, similar to the [Ru(NHC) 4 H] + analogues. Depending on the strength of the agostic interaction a variation of up to 18 ppm in hydride chemical shift is possible and this factor (that is not necessarily readily detected experimentally) can aid in the interpretation of hydride chemical shift data for nominally unsaturated hydride-containing species. The synthesis and crystallographic characterization of the BAr F 4 - salts of [Ru(IMe 4 ) 4 (L)H] + (IMe 4 = 1,3,4,5-tetramethylimidazol-2-ylidene; L = P 4 , SO 2 ; Ar F = 3,5-(CF 3 ) 2 C 6 H 3 ) and [Ru(IMe 4 ) 4 (Cl)H] are also reported.

COMPREHENSIVE ANALYSIS OF BIOLOGICALLY RELEVANT ARSENICALS BY PH-SELECTIVE HYDRIDE GENERATION-ATOMIC ABSORPTION SPECTROMETRY

EPA Science Inventory

A method based on pH-selective generation and separation of arsines is commonly used for analysis of inorganic, methylated, and dimethylated trivalent and pentavalent arsenicals by hydride generation-atomic absorption spectrometry (HG-AAS). We have optimized this method to pe...

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.

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...

Phenolic composition of pomegranate peel extracts using an LC-MS approach with silica hydride columns

USDA-ARS?s Scientific Manuscript database

The peels of different pomegranate cultivars (Molla Nepes, Parfianka, Purple Heart, Wonderful and Vkunsyi) were compared in terms of phenolic composition and total phenolics. Analyses were performed on two silica hydride-based stationary phases: phenyl and undecenoic acid columns. Quantitation was ...

Electrochemical hydrogen Storage Systems

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

Dr. Digby Macdonald

2010-08-09

As the global need for energy increases, scientists and engineers have found a possible solution by using hydrogen to power our world. Although hydrogen can be combusted as a fuel, it is considered an energy carrier for use in fuel cells wherein it is consumed (oxidized) without the production of greenhouse gases and produces electrical energy with high efficiency. Chemical storage of hydrogen involves release of hydrogen in a controlled manner from materials in which the hydrogen is covalently bound. Sodium borohydride and aminoborane are two materials given consideration as chemical hydrogen storage materials by the US Department of Energy.more » A very significant barrier to adoption of these materials as hydrogen carriers is their regeneration from 'spent fuel,' i.e., the material remaining after discharge of hydrogen. The U.S. Department of Energy (DOE) formed a Center of Excellence for Chemical Hydrogen Storage, and this work stems from that project. The DOE has identified boron hydrides as being the main compounds of interest as hydrogen storage materials. The various boron hydrides are then oxidized to release their hydrogen, thereby forming a 'spent fuel' in the form of a lower boron hydride or even a boron oxide. The ultimate goal of this project is to take the oxidized boron hydrides as the spent fuel and hydrogenate them back to their original form so they can be used again as a fuel. Thus this research is essentially a boron hydride recycling project. In this report, research directed at regeneration of sodium borohydride and aminoborane is described. For sodium borohydride, electrochemical reduction of boric acid and sodium metaborate (representing spent fuel) in alkaline, aqueous solution has been investigated. Similarly to literature reports (primarily patents), a variety of cathode materials were tried in these experiments. Additionally, approaches directed at overcoming electrostatic repulsion of borate anion from the cathode, not described in the previous literature for electrochemical reduction of spent fuels, have been attempted. A quantitative analytical method for measuring the concentration of sodium borohydride in alkaline aqueous solution has been developed as part of this work and is described herein. Finally, findings from stability tests for sodium borohydride in aqueous solutions of several different compositions are reported. For aminoborane, other research institutes have developed regeneration schemes involving tributyltin hydride. In this report, electrochemical reduction experiments attempting to regenerate tributyltin hydride from tributyltin chloride (a representative by-product of the regeneration scheme) are described. These experiments were performed in the non-aqueous solvents acetonitrile and 1,2-dimethoxyethane. A non-aqueous reference electrode for electrolysis experiments in acetonitrile was developed and is described. One class of boron hydrides, called polyhedral boranes, became of interest to the DOE due to their ability to contain a sufficient amount of hydrogen to meet program goals and because of their physical and chemical safety attributes. Unfortunately, the research performed here has shown that polyhedral boranes do not react in such a way as to allow enough hydrogen to be released, nor do they appear to undergo hydrogenation from the spent fuel form back to the original hydride. After the polyhedral boranes were investigated, the project goals remained the same but the hydrogen storage material was switched by the DOE to ammonia borane. Ammonia borane was found to undergo an irreversible hydrogen release process, so a direct hydrogenation was not able to occur. To achieve the hydrogenation of the spent ammonia borane fuel, an indirect hydrogenation reaction is possible by using compounds called organotin hydrides. In this process, the organotin hydrides will hydrogenate the spent ammonia borane fuel at the cost of their own oxidation, which forms organotin halides. To enable a closed-loop cycle, our task was then to be able to hydrogenate the organotin halides back to their hydride form. In addition to this experimental work, a parallel project was carried out to develop a new model of electrochemical impedance spectroscopy (EIS) that could be used to define the mechanisms of the electrochemical hydrogenation reactions. The EIS technique is capable of probing complex chemical and electrochemical reactions, and our model was written into a computer code that allowed the input of experimental EIS data and the extraction of kinetic parameters based on a best-fit analysis of theoretical reaction schemes. Finally, electrochemical methods for hydrogenating organic and metallo-organic materials have been explored.« less

Lunar-derived titanium alloys for hydrogen storage

NASA Technical Reports Server (NTRS)

Love, S.; Hertzberg, A.; Woodcock, G.

1992-01-01

Hydrogen gas, which plays an important role in many projected lunar power systems and industrial processes, can be stored in metallic titanium and in certain titanium alloys as an interstitial hydride compound. Storing and retrieving hydrogen with titanium-iron alloy requires substantially less energy investment than storage by liquefaction. Metal hydride storage systems can be designed to operate at a wide range of temperatures and pressures. A few such systems have been developed for terrestrial applications. A drawback of metal hydride storage for lunar applications is the system's large mass per mole of hydrogen stored, which rules out transporting it from earth. The transportation problem can be solved by using native lunar materials, which are rich in titanium and iron.

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.

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.

Hydrogen storage compositions

DOEpatents

Li, Wen; Vajo, John J.; Cumberland, Robert W.; Liu, Ping

2011-04-19

Compositions for hydrogen storage and methods of making such compositions employ an alloy that exhibits reversible formation/deformation of BH.sub.4.sup.- anions. The composition includes a ternary alloy including magnesium, boron and a metal and a metal hydride. The ternary alloy and the metal hydride are present in an amount sufficient to render the composition capable of hydrogen storage. The molar ratio of the metal to magnesium and boron in the alloy is such that the alloy exhibits reversible formation/deformation of BH.sub.4.sup.- anions. The hydrogen storage composition is prepared by combining magnesium, boron and a metal to prepare a ternary alloy and combining the ternary alloy with a metal hydride to form the hydrogen storage composition.

Merging C-H activation and alkene difunctionalization at room temperature: a palladium-catalyzed divergent synthesis of indoles and indolines.

PubMed

Manna, Manash Kumar; Hossian, Asik; Jana, Ranjan

2015-02-06

A palladium-catalyzed 1,2-carboamination through C-H activation at room temperature is reported for the synthesis of 2-arylindoles, and indolines from readily available, inexpensive aryl ureas and vinyl arenes. The reaction initiates with a urea-directed electrophilic ortho palladation, alkene insertion, and β-hydride elimination sequences to provide the Fujiwara-Moritani arylation product. Subsequently, aza-Wacker cyclization, and β-hydride elimination provide the 2-arylindoles in high yields. Intercepting the common σ-alkyl-Pd intermediate, corresponding indolines are also achieved. The indoline formation is attributed to the generation of stabilized, cationic π-benzyl-Pd species to suppress β-hydride elimination.

Method and apparatus for thermal energy storage. [Patent application

DOEpatents

Gruen, D.M.

1975-08-19

A method and apparatus for storing energy by converting thermal energy to potential chemically bound energy in which a first metal hydride is heated to dissociation temperature, liberating hydrogen gas which is compressed and reacted with a second metal to form a second metal hydride while releasing thermal energy. Cooling the first metal while warming the second metal hydride to dissociation temperature will reverse the flow of hydrogen gas back to the first metal, releasing additional thermal energy. The method and apparatus are particularly useful for the storage and conversion of thermal energy from solar heat sources and for the utilization of this energy for space heating purposes, such as for homes or offices.

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.

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.

Precipitation hardening austenitic superalloys

DOEpatents

Korenko, Michael K.

1985-01-01

Precipitation hardening, austenitic type superalloys are described. These alloys contain 0.5 to 1.5 weight percent silicon in combination with about 0.05 to 0.5 weight percent of a post irradiation ductility enhancing agent selected from the group of hafnium, yttrium, lanthanum and scandium, alone or in combination with each other. In addition, when hafnium or yttrium are selected, reductions in irradiation induced swelling have been noted.

Scandium induced structural transformation and B′:B″ cationic ordering in Pb(Fe{sub 0.5}Nb{sub 0.5})O{sub 3} multiferroic ceramics

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

Mallesham, B.; Ranjith, R., E-mail: ranjith@iith.ac.in; Manivelraja, M.

2014-07-21

The current study explores non-magnetic Sc{sup 3+} induced structural transformation, evolution of local B-site cation ordering and associated effect on ferroelectric phase transition temperature T{sub max} (temperature corresponding to dielectric maxima) on increasing the atom percent of Sc substitution in [Pb(Fe{sub 0.5}Nb{sub 0.5})O{sub 3} (PFN)] ceramics. In this regard, the phase pure Pb[(Fe{sub 0.5−x}Sc{sub x})Nb{sub 0.5}]O{sub 3} ceramics with x varying from 0 to 0.5 were synthesized through solid state reaction route. The detailed structural analysis through Rietveld refinement confirms the room temperature transformation from a monoclinic Cm to rhombohedral R3m structure at x = 0.3 mol. % of Sc. Absorption spectra studies showmore » that there is a considerable increment in the bandgap at higher scandium content. Most interestingly, the T{sub max} exhibited an increment for lower scandium contents (x = 0.1 to 0.25) followed by a drop in T{sub max} (x = 0.3 to 0.5). Such anomalous behavior in T{sub max} is expected to arise due to the onset of B′, B″ local cation ordering beyond Sc content x = 0.25. The B-site cation ordering at and beyond x = 0.3 was also confirmed by the evolution of cation order induced Pb-O coupled vibrational mode in Raman scattering studies. In addition, the Mössbauer spectra of PFN (x = 0) and Pb(Fe{sub 0.4}Sc{sub 0.1}Nb{sub 0.5})O{sub 3} (x = 0.1) are reported to verify the spin state and oxidation state of iron. The lattice distortion due to the radius ratio difference between a Sc{sup 3+} cation and Fe{sup 3+} cation in low spin state is responsible for the structural transformation, which in turn facilitates a B′:B″ cation ordering.« less

Electrochromic materials, devices and process of making

DOEpatents

Richardson, Thomas J.

2003-11-11

Thin films of transition metal compositions formed with magnesium that are metals, alloys, hydrides or mixtures of alloys, metals and/or hydrides exhibit reversible color changes on application of electric current or hydrogen. Thin films of these materials are suitable for optical switching elements, thin film displays, sun roofs, rear-view mirrors and architectural glass.

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...

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.

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

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.

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.

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.

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.

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.

Function of Coenzyme F420 in Aerobic Catabolism of 2,4,6-Trinitrophenol and 2,4-Dinitrophenol by Nocardioides simplex FJ2-1A

PubMed Central

Ebert, Sybille; Rieger, Paul-Gerhard; Knackmuss, Hans-Joachim

1999-01-01

2,4,6-Trinitrophenol (picric acid) and 2,4-dinitrophenol were readily biodegraded by the strain Nocardioides simplex FJ2-1A. Aerobic bacterial degradation of these π-electron-deficient aromatic compounds is initiated by hydrogenation at the aromatic ring. A two-component enzyme system was identified which catalyzes hydride transfer to picric acid and 2,4-dinitrophenol. Enzymatic activity was dependent on NADPH and coenzyme F420. The latter could be replaced by an authentic preparation of coenzyme F420 from Methanobacterium thermoautotrophicum. One of the protein components functions as a NADPH-dependent F420 reductase. A second component is a hydride transferase which transfers hydride from reduced coenzyme F420 to the aromatic system of the nitrophenols. The N-terminal sequence of the F420 reductase showed high homology with an F420-dependent NADP reductase found in archaea. In contrast, no N-terminal similarity to any known protein was found for the hydride-transferring enzyme. PMID:10217752

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.

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.

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.

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

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.

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

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

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

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.

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.

EuNi 5 InH 1.5-x (x = 0–1.5): hydrogen induced structural and magnetic transitions

DOE PAGES

Bigun, Inna; Smetana, Volodymyr; Mudryk, Yaroslav; ...

2017-01-01

The new quaternary hydride EuNi 5InH 1.5 has been obtained by hydrogenation of the intermetallic parent EuNi5In under extremely mild conditions, hence, at room temperature and low hydrogen pressure. Hydrogenation at slightly elevated temperatures and pressures allows for the growth of large crystals, which is a rare observation for intermetallic hydrides. EuNi 5InH 1.5 crystallizes in its own structure type ( hP17, P6¯m2, a = 4.9437(6), c = 10.643(1) Å) with a unique arrangement of the intermetallic host. The hydrogen atoms prefer Ni-surrounded positions, occupying {EuNi 3} and {Eu 2Ni 2} tetrahedral voids in the structure. Upon hydrogenation of EuNimore » 5In an anisotropic volume expansion accompanied with a decrease of symmetry is observed. Magnetic measurements reveal antiferromagnetic ordering in the hydride below 4 K and indicate an intermediate +II/+III oxidation state for Eu both in the intermetallic phase and the hydride. X-ray photoemission spectroscopy confirms the existence of the two different oxidation states of Eu. The hydrogenation does not affect the oxidation state of Eu and the type of magnetic ordering, but exerts a strong influence on the transition temperature, crystal structure, mechanical and electrical properties. Crystallographic analysis suggests that Eu(II) and Eu(III) do not order but rather mix homogeneously on crystallographic sites. Electronic structure calculations reveal the metallic character of the hydride with several different types of chemical bonding interactions being present in the compound ranging from the formally ionic Eu–H to covalent Ni–H and delocalized metal–metal. As a result, geometry optimization confirm the thermodynamic instability of the intermetallic host lattice for the hydride and supports a transformation into the parental structure as observed experimentally.« less

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

PubMed

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

1990-10-18

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

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

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

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

Jason D. Hales; Veena Tikare

2014-04-01

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

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

Zidan, Ragaiy

A process of using an electrochemical cell to generate aluminum hydride (AlH.sub.3) and other high capacity hydrides is provided. The electrolytic cell uses an electro-catalytic-additive within a polar non-salt containing solvent to solubilize an ionic hydride such as NaAlH.sub.4 or LiAlH.sub.4. The resulting electrochemical process results in the formation of AlH.sub.3 adduct. AlH.sub.3 is obtained from the adduct by heating under vacuum. 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 or LiAlH.sub.4 as part of a closed loop process of AlH.sub.3 generation.

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.

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.

Phosphors containing boron and metals of Group IIIA and IIIB

DOEpatents

Setlur, Anant Achyut; Srivastava, Alok Mani; Comanzo, Holly Ann; Manivannan, Venkatesan

2006-10-31

A phosphor comprises: (a) at least a first metal selected from the group consisting of yttrium and elements of lanthanide series other than europium; (b) at least a second metal selected from the group consisting of aluminum, gallium, indium, and scandium; (c) boron; and (d) europium. The phosphor is used in light source that comprises a UV radiation source to convert UV radiation to visible light.

Quantum Electronics in the UK. A National-Survey Conference.

DTIC Science & Technology

1985-10-30

flashlamp pumped chromium action, including transitions in dopants doped gadolinium /scandium/gallium garnet which have not previously shown laser lasers...frac- factors that limit performance. They ture. The Southampton scientists fabri - concluded that excited state absorption, cated the fibers by a...topics such as transverse power on the long wavelength side of a switching waves and cross-talk of bista- Fabry -Perot resonance peak at 844 nm, ble

Sc20C60: a volleyballene

NASA Astrophysics Data System (ADS)

Wang, Jing; Ma, Hong-Man; Liu, Ying

2016-06-01

An exceptionally stable hollow cage containing 20 scandium atoms and 60 carbon atoms has been identified. This Sc20C60 molecular cluster has a Th point group symmetry and a volleyball-like shape that we refer to below as ``Volleyballene''. Electronic structure analysis shows that the formation of delocalized π bonds between Sc atoms and the neighboring pentagonal rings made of carbon atoms is crucial for stabilizing the cage structure. A relatively large HOMO-LUMO gap (~1.4 eV) was found. The results of vibrational frequency analysis and molecular dynamics simulations both demonstrate that this Volleyballene molecule is exceptionally stable.An exceptionally stable hollow cage containing 20 scandium atoms and 60 carbon atoms has been identified. This Sc20C60 molecular cluster has a Th point group symmetry and a volleyball-like shape that we refer to below as ``Volleyballene''. Electronic structure analysis shows that the formation of delocalized π bonds between Sc atoms and the neighboring pentagonal rings made of carbon atoms is crucial for stabilizing the cage structure. A relatively large HOMO-LUMO gap (~1.4 eV) was found. The results of vibrational frequency analysis and molecular dynamics simulations both demonstrate that this Volleyballene molecule is exceptionally stable. Electronic supplementary information (ESI) available: Sc20C60: a Volleyballene_SI. See DOI: 10.1039/c5nr07784b

Aluminum-Scandium: A Material for Semiconductor Packaging

NASA Astrophysics Data System (ADS)

Geissler, Ute; Thomas, Sven; Schneider-Ramelow, Martin; Mukhopadhyay, Biswajit; Lang, Klaus-Dieter

2016-10-01

A well-known aluminum-scandium (Al-Sc) alloy, already used in lightweight sports equipment, is about to be established for use in electronic packaging. One application for Al-Sc alloy is manufacture of bonding wires. The special feature of the alloy is its ability to harden by precipitation. The new bonding wires with electrical conductivity similar to pure Al wires can be processed on common wire bonders for aluminum wedge/wedge (w/w) bonding. The wires exhibit very fine-grained microstructure. Small Al3Sc particles are the main reason for its high strength and prevent recrystallization and grain growth at higher temperatures (>150°C). After the wire-bonding process, the interface is well closed. Reliability investigations by active power cycling demonstrated considerably improved lifetime compared with pure Al heavy wires. Furthermore, the Al-Sc alloy was sputter-deposited onto silicon wafer to test it as chip metallization in copper (Cu) ball/wedge bonding technology. After deposition, the layers exhibited fine-grained columnar structure and small coherent Al3Sc particles with dimensions of a few nanometers. These particles inhibit softening processes such as Al splashing in fine wire bonding processes and increase the thickness of remnant Al under the copper balls to 85% of the initial thickness.

High-Performance, Solution-Processed Quantum Dot Light-Emitting Field-Effect Transistors with a Scandium-Incorporated Indium Oxide Semiconductor.

PubMed

He, Penghui; Jiang, Congbiao; Lan, Linfeng; Sun, Sheng; Li, Yizhi; Gao, Peixiong; Zhang, Peng; Dai, Xingqiang; Wang, Jian; Peng, Junbiao; Cao, Yong

2018-05-22

Light-emitting field-effect transistors (LEFETs) have attained great attention due to their special characteristics of both the switching capacity and the electroluminescence capacity. However, high-performance LEFETs with high mobility, high brightness, and high efficiency have not been realized due to the difficulty in developing high electron and hole mobility materials with suitable band structures. In this paper, quantum dot hybrid LEFETs (QD-HLEFETs) combining high-luminous-efficiency quantum dots (QDs) and a solution-processed scandium-incorporated indium oxide (Sc:In 2 O 3 ) semiconductor were demonstrated. The red QD-HLEFET showed high electrical and optical performance with an electron mobility of 0.8 cm 2 V -1 s -1 , a maximum brightness of 13 400 cd/m 2 , and a maximum external quantum efficiency of 8.7%. The high performance of the QD-HLEFET is attributed to the good energy band matching between Sc:In 2 O 3 and QDs and the balanced hole and electron injection (less exciton nonradiative recombination). In addition, incorporation of Sc into In 2 O 3 can suppress the oxygen vacancy and free carrier generation and brings about excellent current and optical modulation (the on/off current ratio is 10 5 and the on/off brightness ratio is 10 6 ).

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

Radchenko, Valery; Engle, Jonathan Ward; Medvedev, Dmitri G.

Scandium-44 g (half-life 3.97 h) shows promise for application in positron emission tomography (PET), due to favorable decay parameters. One of the sources of 44gSc is the 44Ti/ 44gSc generator, which can conveniently provide this radioisotope on a daily basis at a diagnostic facility. Titanium-44 (half-life 60.0 a), in turn, can be obtained via proton irradiation of scandium metal targets. A substantial 44Ti product batch, however, requires high beam currents, long irradiation times and an elaborate chemical procedure for 44Ti isolation and purification. This study describes the production of a combined 175 MBq (4.7 mCi) batch yield of 44Ti inmore » week long proton irradiations at the Los Alamos Isotope Production Facility (LANL-IPF) and the Brookhaven Linac Isotope Producer (BNL-BLIP). A two-step ion exchange chromatography based chemical separation method is introduced: first, a coarse separation of 44Ti via anion exchange sorption in concentrated HCl results in a 44Tc/Sc separation factor of 10 2–10 3. A second, cation exchange based step in HCl media is then applied for 44Ti fine purification from residual Sc mass. In conclusion, this method yields a 90–97% 44Ti recovery with an overall Ti/Sc separation factor of ≥10 6.« less

Thermal, spectroscopic and laser properties of Nd3+ in gadolinium scandium gallium garnet crystal produced by optical floating zone method

NASA Astrophysics Data System (ADS)

Tian, Li; Wang, Shuxian; Wu, Kui; Wang, Baolin; Yu, Haohai; Zhang, Huaijin; Cai, Huaqiang; Huang, Hui

2013-12-01

A neodymium-doped gadolinium scandium gallium garnet (Nd:GSGG) single crystal with dimensions of Φ 5 × 20 mm2 has been grown by means of optical floating zone (OFZ). X-ray powder diffraction (XRPD) result shows that the as-grown Nd:GSGG crystal possesses a cubic structure with space group Ia3d and a cell parameter of a = 1.2561 nm. Effective elemental segregation coefficients of the Nd:GSGG as-grown crystal were calculated by using X-ray fluorescence (XRF). The thermal properties of the Nd:GSGG crystal were systematically studied by measuring the specific heat, thermal expansion and thermal diffusion coefficient, and the thermal conductivity of this crystal was calculated. The absorption and luminescence spectra of Nd:GSGG were measured at room temperature (RT). By using the Judd-Ofelt (J-O) theory, the theoretical radiative lifetime was calculated and compared with the experimental result. Continuous wave (CW) laser performance was achieved with the Nd:GSGG at the wavelength of 1062 nm when it was pumped by a laser diode (LD). A maximum output power of 0.792 W at 1062 nm was obtained with a slope efficiency of 11.89% under a pump power of 7.36 W, and an optical-optical conversion efficiency of 11.72%.

Momentum Distribution as a Fingerprint of Quantum Delocalization in Enzymatic Reactions: Open-Chain Path-Integral Simulations of Model Systems and the Hydride Transfer in Dihydrofolate Reductase.

PubMed

Engel, Hamutal; Doron, Dvir; Kohen, Amnon; Major, Dan Thomas

2012-04-10

The inclusion of nuclear quantum effects such as zero-point energy and tunneling is of great importance in studying condensed phase chemical reactions involving the transfer of protons, hydrogen atoms, and hydride ions. In the current work, we derive an efficient quantum simulation approach for the computation of the momentum distribution in condensed phase chemical reactions. The method is based on a quantum-classical approach wherein quantum and classical simulations are performed separately. The classical simulations use standard sampling techniques, whereas the quantum simulations employ an open polymer chain path integral formulation which is computed using an efficient Monte Carlo staging algorithm. The approach is validated by applying it to a one-dimensional harmonic oscillator and symmetric double-well potential. Subsequently, the method is applied to the dihydrofolate reductase (DHFR) catalyzed reduction of 7,8-dihydrofolate by nicotinamide adenine dinucleotide phosphate hydride (NADPH) to yield S-5,6,7,8-tetrahydrofolate and NADP(+). The key chemical step in the catalytic cycle of DHFR involves a stereospecific hydride transfer. In order to estimate the amount of quantum delocalization, we compute the position and momentum distributions for the transferring hydride ion in the reactant state (RS) and transition state (TS) using a recently developed hybrid semiempirical quantum mechanics-molecular mechanics potential energy surface. Additionally, we examine the effect of compression of the donor-acceptor distance (DAD) in the TS on the momentum distribution. The present results suggest differential quantum delocalization in the RS and TS, as well as reduced tunneling upon DAD compression.

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.

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...

Regeneration of polyborazylene

DOEpatents

Davis, Benjamin L.; Gordon, John C.

2010-12-07

Method of producing ammonia borane, comprising providing polyborazylene; digesting the polyborazylene with a dithiol-containing agent to produce a boro-sulfide compound and a byproduct; converting the byproduct to the boro-sulfide product of step (b) by reaction with a first alkyl-tin hydride; and, converting the boro-sulfide compound produced in steps (b) and (c) to ammonia borane by reaction with a second alkyl-tin hydride.

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.

Design and Development of a 30 Watt Solid Polymer Electrolyte Fuel Cell Power Source Fueled with Calcium Hydride.

DTIC Science & Technology

1978-12-12

hydri de and its integration with the fuel cell. I The combination of the SPE cel l with a hydride fuel offers -- comparedto batteries -- increased...demand changes without intermediate storage of hydrogen gas. In order to control the reacti on with water the hydri de is contained in a cartridge. The use

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...

Mechanism of the sulfurisation of phosphines and phosphites using 3-amino-1,2,4-dithiazole-5-thione (xanthane hydride).

PubMed

Hanusek, Jirí; Russell, Mark A; Laws, Andrew P; Jansa, Petr; Atherton, John H; Fettes, Kevin; Page, Michael I

2007-02-07

Contrary to a previous report, the sulfurisation of phosphorus(III) derivatives by 3-amino-1,2,4-dithiazole-5-thione (xanthane hydride) does not yield carbon disulfide and cyanamide as the additional reaction products. The reaction of xanthane hydride with triphenyl phosphine or trimethyl phosphite yields triphenyl phosphine sulfide or trimethyl thiophosphate, respectively, and thiocarbamoyl isothiocyanate which has been trapped with nucleophiles. The reaction pathway involves initial nucleophilic attack of the phosphorus at sulfur next to the thiocarbonyl group of xanthane hydride followed by decomposition of the phosphonium intermediate formed to products. The Hammett rho-values for the sulfurisation of substituted triphenyl phosphines and triphenyl phosphites in acetonitrile are approximately -1.0. The entropies of activation are very negative (-114+/-15 J mol-1 K-1) with little dependence on solvent which is consistent with a bimolecular association step leading to the transition state. The negative values of DeltaS(not equal) and rho values indicate that the rate limiting step of the sulfurisation reaction is formation of the phosphonium ion intermediate which has an early transition state with little covalent bond formation. The site of nucleophilic attack has been also confirmed using computational calculations.

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

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.

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

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 .

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.

Analysis of Ni-HYDRIDE Thin Film after Surface Plasmon Generation by Laser Technique

NASA Astrophysics Data System (ADS)

Violante, V.; Castagna, E.; Sibilia, C.; Paoloni, S.; Sarto, F.

2005-12-01

A nickel hydride thin film was studied by the attenuated total reflection method. The differences in behavior between a "black" film, and a pure nickel film "blank," are shown. The black nickel hydride film has been obtained by a short electrolysis with 1 M Li2SO4 electrolyte in light water, A shift in the minimum of the observed reflected light occurs, together with a change in the minimum shape (i.e. its half-height width increases). These two phenomenon are due to the change in the electronic band structure of the metal induced by electrons added to the lattice by hydrogen. The change of the electronic structure, revealed by the laser coupling conditions, leads us to consider that a hydride phase was created. Both the blank (not hydrogenated) and black (hydrogenated) specimens were taken under He-Ne laser beam at the reflectance minimum angle for about three hours. A SIMS analysis was also implemented to reveal differences in the isotopic composition of Cu, as marker element between the blank and black films, in order to study the coupled effect of electrolysis and plasmon-polariton excitation on LENR processes in condensed matter.

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

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.

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.

Determination of As, Sb, Bi and Hg in water samples by flow-injection inductively coupled plasma mass spectrometry with an in-situ nebulizer/hydride generator

NASA Astrophysics Data System (ADS)

Chen, Chih-Shyue; Jiang, Shiuh-Jen

1996-12-01

A simple and very inexpensive in-situ nebulizer/hydride generator was used with inductively coupled plasma mass spectrometry (ICP-MS) for the determination of As, Sb, Bi and Hg in water samples. The application of hydride generation ICP-MS alleviated the sensitivity problem of As, Sb, Bi and Hg determinations encountered when the conventional pneumatic nebulizer was used for sample introduction. The sample was introduced by flow injection to minimize the deposition of solids on the sampling orifice. The elements in the sample were reduced to the lower oxidation states with L-cysteine before being injected into the hydride generation system. This method has a detection limit of 0.003, 0.003, 0.017 and 0.17 ng ml -1 for As, Bi, Sb and Hg, respectively. This method was applied to determine As, Sb, Bi and Hg in a CASS-3 nearshore seawater reference sample, a SLRS-2 riverine water reference sample and a tap water collected from National Sun Yat-Sen University. The concentrations of the elements were determined by standard addition method. The precision was better than 20% for most of the determinations.

High magnetic-refrigeration performance of plate-shaped La{sub 0.5}Pr{sub 0.5}Fe{sub 11.4}Si{sub 1.6} hydrides sintered in high-pressure H{sub 2} atmosphere

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

Sun, N. K., E-mail: naikunsun@163.com; Guo, J.; Zhao, X. G., E-mail: xgzhao@imr.ac.cn

2015-03-02

La(Fe, Si){sub 13} hydride is regarded as one of the most promising room-temperature refrigerants. However, to use the alloys in an active magnetic regenerator machine, it is vital to prepare thin refrigerants. In this work, a high H{sub 2} gas pressure of 50 MPa was employed to suppress the desorption of hydrogen atoms during the sintering process of plate-shaped La{sub 0.5}Pr{sub 0.5}Fe{sub 11.4}Si{sub 1.6} hydrides. At 330 K, a high-density sintered thin plate shows a large magnetic-entropy change ΔS{sub m} of 15.5 J/kg K (106 mJ/cm{sup 3 }K) for a field change of 2 T. The volumetric ΔS{sub m} is almost twice as large as that ofmore » bonded La(Fe,Si){sub 13} hydrides. Favorably, hysteresis is almost absent due to the existence of micropores with a porosity of 0.69% which has been analyzed with high-resolution X-ray microtomography.« less

Effect of the oxidation front penetration on in-clad hydrogen migration

NASA Astrophysics Data System (ADS)

Feria, F.; Herranz, L. E.

2018-03-01

In LWR fuel claddings the embrittlement due to hydrogen precipitates (i.e., hydrides) is a degrading mechanism that concerns in nuclear safety, particularly in dry storage. A relevant factor is the radial distribution of the hydrogen absorbed, especially the hydride rim formed. Thus, a reliable assessment of fuel performance should account for hydrogen migration. Based on the current state of modelling of hydrogen dynamics in the cladding, a 1D radial model has been derived and coupled with the FRAPCON code. The model includes the effect of the oxidation front progression on in-clad hydrogen migration, based on experimental observations found (i.e., dissolution/diffusion/re-precipitation of the hydrogen in the matrix ahead of the oxidation front). A remarkable quantitative impact of this new contribution has been shown by analyzing the hydrogen profile across the cladding of several high burnup fuel scenarios (>60 GW d/tU); other potential contributions like thermodiffusion and diffusion in the hydride phase hardly make any difference. Comparisons against PIE measurements allow concluding that the model accuracy notably increases when the effect of the oxidation front is accounted for in the hydride rim formation. In spite of the promising results, further validation would be needed.

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.

Stress corrosion cracking of titanium alloys

NASA Technical Reports Server (NTRS)

May, R. C.; Beck, F. H.; Fontana, M. G.

1971-01-01

Experiments were conducted to study (1) the basic electrochemical behavior of titanium in acid chloride solutions and (2) the response of the metal to dynamic straining in the same evironment. The aim of this group of experiments was to simulate, as nearly as possible, the actual conditions which exist at the tip of a crack. One of the foremost theories proposed to explain the propagation of stress corrosion cracks is a hydrogen embrittlement theory involving the precipitation of embrittling titanium hydrides inside the metal near the crack tip. An initial survey of the basic electrochemical literature indicated that surface hydrides play a critical role in the electrochemistry of titanium in acid solutions. A comprehensive analysis of the effect of surface films, particularly hydrides, on the electrochemical behavior of titanium in these solution is presented.

Mechanistic Studies at the Interface Between Organometallic Chemistry and Homogeneous Catalysis

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

Casey, Charles P

Mechanistic Studies at the Interface Between Organometallic Chemistry and Homogeneous Catalysis Charles P. Casey, Principal Investigator Department of Chemistry, University of Wisconsin - Madison, Madison, Wisconsin 53706 Phone 608-262-0584 FAX: 608-262-7144 Email: casey@chem.wisc.edu http://www.chem.wisc.edu/main/people/faculty/casey.html Executive Summary. Our goal was to learn the intimate mechanistic details of reactions involved in homogeneous catalysis and to use the insight we gain to develop new and improved catalysts. Our work centered on the hydrogenation of polar functional groups such as aldehydes and ketones and on hydroformylation. Specifically, we concentrated on catalysts capable of simultaneously transferring hydride from a metal center and a proton frommore » an acidic oxygen or nitrogen center to an aldehyde or ketone. An economical iron based catalyst was developed and patented. Better understanding of fundamental organometallic reactions and catalytic processes enabled design of energy and material efficient chemical processes. Our work contributed to the development of catalysts for the selective and mild hydrogenation of ketones and aldehydes; this will provide a modern green alternative to reductions by LiAlH4 and NaBH4, which require extensive work-up procedures and produce waste streams. (C5R4OH)Ru(CO)2H Hydrogenation Catalysts. Youval Shvo described a remarkable catalytic system in which the key intermediate (C5R4OH)Ru(CO)2H (1) has an electronically coupled acidic OH unit and a hydridic RuH unit. Our efforts centered on understanding and improving upon this important catalyst for reduction of aldehydes and ketones. Our mechanistic studies established that the reduction of aldehydes by 1 to produce alcohols and a diruthenium bridging hydride species occurs much more rapidly than regeneration of the ruthenium hydride from the diruthenium bridging hydride species. Our mechanistic studies require simultaneous transfer of hydride from ruthenium to the aldehyde carbon and of a proton from the CpOH unit to the aldehyde oxygen and support reduction of the aldehyde without its prior coordination to ruthenium. Another important step in the catalysis is the regeneration of 1 from reaction of H2 with the stable diruthenium bridging hydride complex 2. Studies of the microscopic reverse of this process (hydrogen evolution from 1 which occurs at 80°C) in the presence of alcohol (the product of aldehyde hydrogenation) have shown that a dihydrogen complex is formed reversibly at a rate much faster than hydrogen evolution. Kinetic and theoretical studies in collaboration with Professor Qiang Cui of Wisconsin indicated an important role for alcohol in mediating transfer of hydrogen to ruthenium. One key to developing more active catalysts was to destabilize the bridging hydride intermediate 2 to prevent its formation or to speed its conversion to a reactive monohydride 1 by reaction with H2. We found several successful ways to destabilize the bridging hydride and to obtain more active catalysts. Most recently, we discovered related iron catalysts for hydrogenation that do not form dimers; the cost advantage of iron catalysts is spectacular. Iron Catalysts. In an exciting development, we found that a related iron complex is also a very active ketone hydrogenation catalyst. This hydrogenation catalyst shows high chemoselectivity for aldehydes, ketones, and imines and isolated C=C, CºC, C-X, -NO2, epoxides, and ester functions are unaffected by the hydrogenation conditions. Mechanistic studies have established a reversible hydrogen transfer step followed by rapid dihydrogen activation. The same iron complex also catalyzes transfer hydrogenation of ketones.« less

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 migration. Enantioselective reactions of α-alkyl-α-diazocarbonyl compounds have been developed using bimetallic N-imido-tert-leucinate-derived complexes. The most effective complexes were found by computation and X-ray crystallography to adopt a "chiral crown" conformation in which all of the imido groups are presented on one face of the paddlewheel complex in a chiral arrangement. Insight from computational studies guided the design and synthesis of a mixed ligand paddlewheel complex, Rh2(S-PTTL)3TPA, the structure of which bears similarity to the chiral crown complex Rh2(S-PTTL)4. Rh2(S-PTTL)3TPA engages substrate classes (aliphatic alkynes, silylacetylenes, α-olefins) that are especially challenging in intermolecular reactions of α-alkyl-α-diazoesters and catalyzes enantioselective cyclopropanation, cyclopropenation, and indole C-H functionalization with yields and enantioselectivities that are comparable or superior to Rh2(S-PTTL)4. The work detailed in this Account describes progress toward enabling a more general utility for α-alkyl-α-diazo compounds in Rh-catalyzed carbene reactions. Further studies on ligand design and synthesis will continue to broaden the scope of their selective reactions.

Nanocomposites for Electronic Applications. Volume 1

DTIC Science & Technology

1993-06-14

for a PZT thin film micro- motor using a rotating flexure wave generated in a PZT film on a silicon oxynitride diaphragm. The rotating wave has been...Solid State Science, The Pennsylvania State University (May 1992). 6. Jayne R. Giniewicz. "An Investigation of the Lead Scandium Tantalate-Lead...Materials and Structures, SPIE, Albuquerque, NM (February 1-4, 1993). 24. G. Harshe, J. P. Dougherty, and R. E. Newnham. "Theoretical Modelling of 3-0/0-3

Obsidian sources characterized by neutron-activation analysis.

PubMed

Gordus, A A; Wright, G A; Griffin, J B

1968-07-26

Concentrations of elements such as manganese, scandium, lanthanum, rubidium, samarium, barium, and zirconium in obsidian samples from different flows show ranges of 1000 percent or more, whereas the variation in element content in obsidian samples from a single flow appears to be less than 40 percent. Neutron-activation analysis of these elements, as well as of sodium and iron, provides a means of identifying the geologic source of an archeological artifact of obsidian.

Mineral resource of the month: rare earth elements

USGS Publications Warehouse

,

2011-01-01

The article provides information on rare earth elements, which are group of 17 natural metallic elements. The rare earth elements are scandium, yttrium and lanthanides and classified into light rare earth elements (LREE) and heavy rate earth elements (HREE). The principal ores of the rare earth elements are identified. An overview of China's production of 97 percent of the rare earths in the world is provided. Commercial applications of rare earths are described.

Origin of howardites, diogenites and eucrites - A mass balance constraint

NASA Technical Reports Server (NTRS)

Warren, P. H.

1985-01-01

Two petrogenetic models for the noncumulate-basaltic parts of howardite meteorites are discussed. A mass balance constraint is developed which indicates that more than half of the basaltic components in howardites formed as residual liquids from fractional crystallization of melts that had earlier produced diogentelike pyroxene cumulate components. Other model constriants involving scandium trends, clustering near olivine-pyroxene-plagioclase peritectic, and MgO/(MgO + FeO) ratios are discussed.

Cobalt and scandium partitioning versus iron content for crystalline phases in ultramafic nodules

USGS Publications Warehouse

Glassley, W.E.; Piper, D.Z.

1978-01-01

Fractionation of Co and Sc between garnets, olivines, and clino- and orthopyroxenes, separated from a suite of Salt Lake Crater ultramafic nodules that equilibrated at the same T and P, is strongly dependent on Fe contents. This observation suggests that petrogenetic equilibrium models of partial melting and crystal fractionation must take into account effects of magma composition, if they are to describe quantitatively geochemical evolutionary trends. ?? 1978.

Cr-doped scandium borate laser

DOEpatents

Chai, Bruce H.; Lai, Shui T.; Long, Margaret N.

1989-01-01

A broadly wavelength-tunable laser is provided which comprises as the laser medium a single crystal of MBO.sub.3 :Cr.sup.3+, where M is selected from the group of Sc, In and Lu. The laser may be operated over a broad temperature range from cryogenic temperatures to elevated temperatures. Emission is in a spectral range from red to infrared, and the laser is useful in the fields of defense, communications, isotope separation, photochemistry, etc.

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.

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.

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...

Electrochemical preparation of tris(tert-butyldimethylsilyl)cyclopropene and its hydride abstraction to tris(tert-butyldimethylsilyl)cyclopropenium tetrafluoroborate

PubMed Central

Buchholz, Herwig A.; Prakash, G. K. Surya; Deffieux, Denis; Olah, George A.

1999-01-01

Electrochemical reductive tert-butyldimethylsilylation of tetrachlorocyclopropene to 1,2,3-tris(tert-butyldimethylsilyl)cyclopropene, a potential strained precursor for Diels–Alder and related cycloaddition reactions, is described. By hydride abstraction with nitrosonium tetrafluoroborate, 1,2,3-tris(tert-butyldimethylsilyl)cyclopropene is ionized quantitatively to Hückeloid 2π aromatic tris(tert-butyldimethylsilyl)cyclopropenium tetrafluoroborate. PMID:10468551

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

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.

Hydrogen release reactions of Al-based complex hydrides enhanced by vibrational dynamics and valences of metal cations

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

Sato, T.; Ramirez-Cuesta, Anibal J.; Daemen, Luke L.

2016-08-31

Hydrogen release from Al-based complex hydrides composed of metal cation(s) and [AlH4] – was investigated using inelastic neutron scattering viewed from vibrational dynamics. Here, the hydrogen release followed the softening of translational and [AlH4] – librational modes, which was enhanced by vibrational dynamics and the valence(s) of the metal cation(s).

METHOD FOR TESTING COATINGS

DOEpatents

Johns, I.B.; Newton, A.S.

1958-09-01

A method is described for detecting pin hole imperfections in coatings on uranium-metal objects. Such coated objects are contacted with a heated atmosphere of gaseous hydrogen and imperfections present in the coatings will allow the uranlum to react with the hydrogen to form uranium hydride. Since uranium hydride is less dense than uranium metal it will swell, causing enlargement of the coating defeot and rendering it visible.

Insights to Superconducting Radio-Frequency Cavity Processing from First Principles Calculations and Spectroscopic Techniques

NASA Astrophysics Data System (ADS)

Ford, Denise Christine

Insights to the fundamental processes that occur during the manufacturing of niobium superconducting radio-frequency (SRF) cavities are provided via analyses of density functional theory calculations and Raman, infrared, and nuclear magnetic resonance (NMR) spectra. I show that during electropolishing fluorine is bound and released by the reaction of the acid components in the solution: HF + H2SO4 <-> HFSO3 + H2O. This result implies that new recipes can possibly be developed on the principle of controlled release of fluorine by a chemical reaction. I also show that NMR or Raman spectroscopy can be used to monitor the free fluorine when polishing with the standard electropolishing recipe. Density functional theory was applied to calculate the properties of common processing impurities---hydrogen, oxygen, nitrogen, and carbon---in the niobium. These impurities lower the superconducting transition temperature of niobium, and hydride precipitates are at best weakly superconducting. I modeled several of the niobium hydride phases relevant to SRF cavities, and explain the phase changes in the niobium hydrogen system based on the charge transfer between niobium and hydrogen and the strain field inside of the niobium. I also present evidence for a niobium lattice vacancy serving as a nucleation center for hydride phase formation. In considering the other chemical impurities in niobium, I show that the absorption of oxygen into a niobium lattice vacancy is preferred over the absorption of hydrogen, which indicates that oxygen can block these phase nucleation centers. I also show that dissolved oxygen atoms can trap dissolved hydrogen atoms to prevent niobium hydride phase formation. Nitrogen and carbon were studied in less depth, but behaved similarly to oxygen. Based on these results and a literature survey, I propose a mechanism for the success of the low-temperature anneal applied to niobium SRF cavities. Finally, I present the beginning of a model to describe magnetic impurities in niobium SRF cavities, which can cause a loss of local superconductivity. I calculated magnetic configurations of niobium hydrides and oxides, and show that stoichiometric hydride and oxide structures are nonmagnetic, but defective oxide structures retain local magnetic moments.

Isolation, observation, and computational modeling of proposed intermediates in catalytic proton reductions with the hydrogenase mimic Fe2(CO)6S2C6H4.

PubMed

Wright, Robert J; Zhang, Wei; Yang, Xinzheng; Fasulo, Meg; Tilley, T Don

2012-01-07

Proposed electrocatalytic proton reduction intermediates of hydrogenase mimics were synthesized, observed, and studied computationally. A new mechanism for H(2) generation appears to involve Fe(2)(CO)(6)(1,2-S(2)C(6)H(4)) (3), the dianions {[1,2-S(2)C(6)H(4)][Fe(CO)(3)(μ-CO)Fe(CO)(2)](2-) (3(2-)), the bridging hydride {[1,2-S(2)C(6)H(4)][Fe(CO)(3)(μ-CO)(μ-H)Fe(CO)(2)]}(-), 3H(-)(bridging), and the terminal hydride 3H(-)(term-stag), {[1,2-S(2)C(6)H(4)][HFe(CO)(3)Fe(CO)(3)]}(-), as intermediates. The dimeric sodium derivative of 3(2-), {[Na(2)(THF)(OEt(2))(3)][3(2-)]}(2) (4) was isolated from reaction of Fe(2)(CO)(6)(1,2-S(2)C(6)H(4)) (3) with excess sodium and was characterized by X-ray crystallography. It possesses a bridging CO and an unsymmetrically bridging dithiolate ligand. Complex 4 reacts with 4 equiv. of triflic or benzoic acid (2 equiv. per Fe center) to generate H(2) and 3 in 75% and 60% yields, respectively. Reaction of 4 with 2 equiv. of benzoic acid generated two hydrides in a 1.7 : 1 ratio (by (1)H NMR spectroscopy). Chemical shift calculations on geometry optimized structures of possible hydride isomers strongly suggest that the main product, 3H(-)(bridging), possesses a bridging hydride ligand, while the minor product is a terminal hydride, 3H(-)(term-stag). Computational studies support a catalytic proton reduction mechanism involving a two-electron reduction of 3 that severs an Fe-S bond to generate a dangling thiolate and an electron rich Fe center. The latter iron center is the initial site of protonation, and this event is followed by protonation at the dangling thiolate to give the thiol thiolate [Fe(2)H(CO)(6)(1,2-SHSC(6)H(4))]. This species then undergoes an intramolecular acid-base reaction to form a dihydrogen complex that loses H(2) and regenerates 3.