Science.gov

Sample records for alkaline earth hydrides

  1. Alkaline-earth metal hydrides as novel host lattices for Eu(II) luminescence.

    PubMed

    Kunkel, Nathalie; Kohlmann, Holger; Sayede, Adlane; Springborg, Michael

    2011-07-04

    Luminescence of divalent europium has been investigated for the first time in metal hydrides. A complete solid-solution series was found for the pseudobinary system Eu(x)Sr(1-x)H(2) [a = 637.6(1) pm -12.1(3)x pm, b = 387.0(1)-6.5(2)x pm, c = 732.2(2)-10.1(4)x pm]. Europium-doped alkaline-earth hydrides Eu(x)M(1-x)H(2) (M = Ca, Sr, Ba) with a small europium concentration (x = 0.005) exhibit luminescence with maximum emission wavelengths of 764 nm (M = Ca), 728 nm (M = Sr), and 750 nm (M = Ba); i.e., the emission energy of divalent europium shows an extremely large red shift compared to the emission energies of fluorides or oxides. Theoretical calculations (LDA+U) confirm decreasing band gaps with increasing europium content of the solid solutions.

  2. Microscopic calculation of the compressibility of hydrides of alkaline metals

    NASA Astrophysics Data System (ADS)

    Krymov, V. A.; Fuks, D. L.

    1987-09-01

    Isotherms have been constructed and compressibilities and sound velocities have been calculated for the hydrides of alkaline metals on the basis of the functional theory of the local electron density, within the framework of the pseudopotential method. The expression obtained for the electron density distribution allows one to perform the analysis of the character of the binding forces and to determine the dependence of the degree of ionization on pressure in these compounds.

  3. Molecular rare-earth-metal hydrides in non-cyclopentadienyl environments.

    PubMed

    Fegler, Waldemar; Venugopal, Ajay; Kramer, Mathias; Okuda, Jun

    2015-02-02

    Molecular hydrides of the rare-earth metals play an important role as homogeneous catalysts and as counterparts of solid-state interstitial hydrides. Structurally well-characterized non-metallocene-type hydride complexes allow the study of elementary reactions that occur at rare-earth-metal centers and of catalytic reactions involving bonds between rare-earth metals and hydrides. In addition to neutral hydrides, cationic derivatives have now become available.

  4. Alkaline earth filled nickel skutterudite antimonide thermoelectrics

    DOEpatents

    Singh, David Joseph

    2013-07-16

    A thermoelectric material including a body centered cubic filled skutterudite having the formula A.sub.xFe.sub.yNi.sub.zSb.sub.12, where A is an alkaline earth element, x is no more than approximately 1.0, and the sum of y and z is approximately equal to 4.0. The alkaline earth element includes guest atoms selected from the group consisting of Be, Mb, Ca, Sr, Ba, Ra and combinations thereof. The filled skutterudite is shown to have properties suitable for a wide variety of thermoelectric applications.

  5. Counterion influence on the vibrational wavenumbers in ternary and quaternary metal hydride salts, A2MH6 (A = alkali metal, alkaline earth, and lanthanides; M = Ir, Fe, Ru, Os, Pt, Mn).

    PubMed

    Gilson, Denis F R; Moyer, Ralph O

    2012-02-06

    The wavenumbers of the ν(3) metal-hydrogen stretching mode (T(1u)) in the IR spectra of both ternary and quaternary hexahydrido salts of transition metals from groups 7 to 10 ([Mn(I)H(6)](5-), [Fe(II)H(6)](4-), [Ru(II)H(6)](4-), [Os(II)H(6)](4-), [Ir(III)H(6)](3-), and [Pt(IV)H(6)](2-)) depend linearly upon the ionization energies of the counterions (alkali metal, alkaline earth, and lanthanide) with a separate line for each metal. This relationship provides quantitative support for the charge-transfer mechanism for explaining the stabilities of these compounds.

  6. Alkaline earth metal catalysts for asymmetric reactions.

    PubMed

    Kobayashi, Shū; Yamashita, Yasuhiro

    2011-01-18

    The group 2 alkaline earth metals calcium (Ca), strontium (Sr), and barium (Ba) are among the most common elements on Earth, abundant in both the sea and the Earth's crust. Although they are familiar in our daily lives, their application to organic synthesis has, so far, been limited. Some particularly useful properties of these elements include (i) low electronegativity, (ii) a stable oxidation state of +2, meaning that they can potentially form two covalent bonds with anions, and (iii) the ability to occupy a variety of coordination sites due to their large ionic radius. Furthermore, the alkaline earth metals, found between the group 1 and group 3 elements, show mild but significant Lewis acidity, which can be harnessed to control coordinative molecules via a Lewis acid-base interaction. Taken together, these characteristics make the metals Ca, Sr, and Ba very promising components of highly functionalized acid-base catalysts. In this Account, we describe the development of chiral alkaline earth metal catalysts for asymmetric carbon-carbon bond-forming reactions. Recently prepared chiral alkaline earth metal complexes have shown high diastereo- and enantioselectivities in fundamental and important chemical transformations. We chose chiral bisoxazoline (Box) derivatives bearing a methylene tether as a ligand for chiral modification. These molecules are very useful because they can covalently coordinate to alkaline earth metals in a bidentate fashion through deprotonation of the tether portion. It was found that chiral calcium-Box complexes could successfully promote catalytic asymmetric 1,4-addition and [3 + 2] cycloaddition reactions with high diastereo- and enantioselectivities. Both the calcium-Box complexes and chiral strontium-bis-sulfonamide and chiral barium-BINOLate complexes could catalyze asymmetric 1,4-addition reactions with high enantioselectivities. Furthermore, we designed a calcium-neutral coordinative ligand complex as a new type of chiral alkaline

  7. Geoneutrinos and Hydridic Earth (or primordially hydrogen-rich planet)

    NASA Astrophysics Data System (ADS)

    Bezrukov, L.; Sinev, V.

    2015-03-01

    Geoneutrino is a new channel of information about geochemical composition of the Earth. We analyzed here the following problem. What statistics do we need to distinguish between predictions of Bulk Silicate Earth model and Hydridic Earth model for Th/U signal ratio? We obtained the simple formula for estimation of error of Th/U signal ratio. Our calculations show that we need more than 22 kt · year exposition for Gran-Sasso underground laboratory and Sudbury Neutrino Observatory. We need more than 27 kt · year exposition for Kamioka site in the case of stopping of all Japanese nuclear power plants.

  8. Alkaline and alkaline earth metal phosphate halides and phosphors

    DOEpatents

    Lyons, Robert Joseph; Setlur, Anant Achyut; Cleaver, Robert John

    2012-11-13

    Compounds, phosphor materials and apparatus related to nacaphite family of materials are presented. Potassium and rubidium based nacaphite family compounds and phosphors designed by doping divalent rare earth elements in the sites of alkaline earth metals in the nacaphite material families are descried. An apparatus comprising the phosphors based on the nacaphite family materials are presented herein. The compounds presented is of formula A.sub.2B.sub.1-yR.sub.yPO.sub.4X where the elements A, B, R, X and suffix y are defined such that A is potassium, rubidium, or a combination of potassium and rubidium and B is calcium, strontium, barium, or a combination of any of calcium, strontium and barium. X is fluorine, chlorine, or a combination of fluorine and chlorine, R is europium, samarium, ytterbium, or a combination of any of europium, samarium, and ytterbium, and y ranges from 0 to about 0.1.

  9. The alkaline earth intercalates of molybdenum disulfide

    NASA Technical Reports Server (NTRS)

    Somoano, R. B.; Hadek, V.; Rembaum, A.; Samson, S.; Woollam, J. A.

    1975-01-01

    Molybdenum disulfide has been intercalated with calcium and strontium by means of the liquid ammonia technique. Chemical, X-ray, and superconductivity data are presented. The X-ray data reveal a lowering of crystal symmetry and increase of complexity of the structure upon intercalation with the alkaline earth metals. The Ca and Sr intercalates start to superconduct at 4 and 5.6 K, respectively, and show considerable anisotropy regarding the critical magnetic field.

  10. Alkaline earth cation extraction from acid solution

    DOEpatents

    Dietz, Mark; Horwitz, E. Philip

    2003-01-01

    An extractant medium for extracting alkaline earth cations from an aqueous acidic sample solution is described as are a method and apparatus for using the same. The separation medium is free of diluent, free-flowing and particulate, and comprises a Crown ether that is a 4,4'(5')[C.sub.4 -C.sub.8 -alkylcyclohexano]18-Crown-6 dispersed on an inert substrate material.

  11. Oxidation catalysts on alkaline earth supports

    DOEpatents

    Mohajeri, Nahid

    2017-03-21

    An oxidation catalyst includes a support including particles of an alkaline earth salt, and first particles including a palladium compound on the support. The oxidation catalyst can also include precious metal group (PMG) metal particles in addition to the first particles intermixed together on the support. A gas permeable polymer that provides a continuous phase can completely encapsulate the particles and the support. The oxidation catalyst may be used as a gas sensor, where the first particles are chemochromic particles.

  12. Diclofenac salts. III. Alkaline and earth alkaline salts.

    PubMed

    Fini, Adamo; Fazio, Giuseppe; Rosetti, Francesca; Angeles Holgado, M; Iruín, Ana; Alvarez-Fuentes, Josefa

    2005-11-01

    Diclofenac salts containing the alkaline and two earth alkaline cations have been prepared and characterized by scanning electron microscopy (SEM) and EDAX spectroscopy; and by thermal and thermogravimetric analysis (TGA): all of them crystallize as hydrate when precipitated from water. The salts dehydrate at room temperature and more easily on heating, but recovery the hydration, when placed in a humid environment. X-ray diffraction spectra suggest that on dehydration new peaks appear on diffractograms and the lattice of the salts partially looses crystallinity. This phenomenon is readily visible in the case of the calcium and magnesium salts, whose thermograms display a crystallization exotherm, before melting or decomposing at temperatures near or above 200 degrees C; these last salts appear to form solvates, when prepared from methanol. The thermogram of each salt shows a complex endotherm of dehydration about 100 degrees C; the calcium salt displays two endotherms, well separated at about 120 and 160 degrees C, which disappear after prolonged heating. Decomposition exotherms, before or soon after the melting, appear below 300 degrees C. The ammonium salt is thermally unstable and, when heated to start dehydration, dissociates and leaves acidic diclofenac.

  13. Hydrogen storage of a novel combined system of LiNH2-NaMgH3: synergistic effects of in situ formed alkali and alkaline-earth metal hydrides.

    PubMed

    Li, Yongtao; Fang, Fang; Song, Yun; Li, Yuesheng; Sun, Dalin; Zheng, Shiyou; Bendersky, Leonid A; Zhang, Qingan; Ouyang, Liuzhang; Zhu, Min

    2013-02-07

    Bimetallic hydride NaMgH(3) is used for the first time as a vehicle to enhance hydrogen release and uptake from LiNH(2). The combination of NaMgH(3) with LiNH(2) at a molar ratio of 1 : 2 can release about 4.0 wt% of hydrogen without detectable NH(3) emission in the temperature range of 45 °C to 325 °C and exhibiting superior dehydrogenation as compared to individual NaH and/or MgH(2) combined with LiNH(2). A high capacity retention of about 75% resulting from the introduction of NaMgH(3) is also achieved in LiNH(2) as well as re-hydrogenation under milder conditions of 180 °C and 5 MPa H(2) pressure. These significant improvements are attributed to synergistic effects of in situ formed NaH and MgH(2)via the decomposition of NaMgH(3) where a succession of competing reactions from the cyclic consumption/recovery of NaH are involved and serve as a "carrier" for the ultra-rapid conveyance of the N-containing species between the [NH(2)](-) amide and the resulting [NH](2-) imide complexes.

  14. Superconductivity above the lowest Earth temperature in pressurized sulfur hydride

    NASA Astrophysics Data System (ADS)

    Bianconi, Antonio; Jarlborg, Thomas

    2015-11-01

    A recent experiment has shown a macroscopic quantum coherent condensate at 203 K, about 19 degrees above the coldest temperature recorded on the Earth surface, 184 K (-89.2 ^\\circ \\text{C}, -128.6 ^\\circ \\text{F}) in pressurized sulfur hydride. This discovery is relevant not only in material science and condensed matter but also in other fields ranging from quantum computing to quantum physics of living matter. It has given the start to a gold rush looking for other macroscopic quantum coherent condensates in hydrides at the temperature range of living matter 200c <400 \\text{K} . We present here a review of the experimental results and the theoretical works and we discuss the Fermiology of \\text{H}3\\text{S} focusing on Lifshitz transitions as a function of pressure. We discuss the possible role of the shape resonance near a neck disrupting Lifshitz transition, in the Bianconi-Perali-Valletta (BPV) theory, for rising the critical temperature in a multigap superconductor, as the Feshbach resonance rises the critical temperature in Fermionic ultracold gases.

  15. Neutral binuclear rare-earth metal complexes with four μ₂-bridging hydrides.

    PubMed

    Rong, Weifeng; He, Dongliang; Wang, Meiyan; Mou, Zehuai; Cheng, Jianhua; Yao, Changguang; Li, Shihui; Trifonov, Alexander A; Lyubov, Dmitrii M; Cui, Dongmei

    2015-03-25

    The first neutral rare-earth metal dinuclear dihydrido complexes [(NPNPN)LnH2]2 (2-Ln; Ln = Y, Lu; NPNPN: N[Ph2PNC6H3((i)Pr)2]2) bearing μ2-bridging hydride ligands have been synthesized. In the presence of THF, 2-Y undergoes intramolecular activation of the sp(2) C-H bond to form dinuclear aryl-hydride complex 3-Y containing three μ2-bridging hydride ligands.

  16. Method of increasing the sulfation capacity of alkaline earth sorbents

    DOEpatents

    Shearer, J.A.; Turner, C.B.; Johnson, I.

    1980-03-13

    A system and method for increasing the sulfation capacity of alkaline earth carbonates to scrub sulfur dioxide produced during the fluidized bed combustion of coal in which partially sulfated alkaline earth carbonates are hydrated in a fluidized bed to crack the sulfate coating and convert the alkaline earth oxide to the hydroxide. Subsequent dehydration of the sulfate-hydroxide to a sulfate-oxide particle produces particles having larger pore size, increased porosity, decreased grain size and additional sulfation capacity. A continuous process is disclosed.

  17. Method of increasing the sulfation capacity of alkaline earth sorbents

    DOEpatents

    Shearer, John A.; Turner, Clarence B.; Johnson, Irving

    1982-01-01

    A system and method for increasing the sulfation capacity of alkaline earth carbonates to scrub sulfur dioxide produced during the fluidized bed combustion of coal in which partially sulfated alkaline earth carbonates are hydrated in a fluidized bed to crack the sulfate coating and convert the alkaline earth oxide to the hydroxide. Subsequent dehydration of the sulfate-hydroxide to a sulfate-oxide particle produces particles having larger pore size, increased porosity, decreased grain size and additional sulfation capacity. A continuous process is disclosed.

  18. Study of point defects in alkaline-earth sulfides

    SciTech Connect

    Pandey, R.; Kunz, A.B.; Vail, J.M.

    1988-11-01

    The results of a computer simulation study of point defects including vacancy, interstitial, and F/sup +/ center in alkaline-earth sulfides are presented. The study is based on ICECAP/HADES simulation procedures and uses empirical interionic potentials obtained from the analysis of macroscopic data for these materials. The results predict the dominance of Schottky disorder and suggest that vacancy migration predominates in alkaline-earth sulfides. Furthermore, the calculated F/sup +/ center absorption energy is in good agreement with the experimental data deduced from the optical stimulated studies in these materials.

  19. Tuning NaYF4 Nanoparticles through Alkaline Earth Doping

    PubMed Central

    Chen, Xian; Peng, Dengfeng; Wang, Feng

    2013-01-01

    Phase and size of lanthanide-doped nanoparticles are the most important characteristics that dictate optical properties of these nanoparticles and affect their technological applications. Herein, we present a systematic study to examine the effect of alkaline earth doping on the formation of NaYF4 upconversion nanoparticles. We show that alkaline earth doping has a dual function of tuning particle size of hexagonal phase NaYF4 nanoparticles and stabilizing cubic phase NaYF4 nanoparticles depending on composition and concentration of the dopant ions. The study described here represents a facile and general strategy to tuning the properties of NaYF4 upconversion nanoparticles. PMID:28348353

  20. 40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting...

  1. 40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting...

  2. 40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting...

  3. 40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting...

  4. 40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting...

  5. Specialties of distributions of alkaline-earth metals in coal

    SciTech Connect

    Fan Jinchuan; Fan Minqiang

    1997-12-31

    Four different ranks of coal have been sampled and separated into different density fractions by Float-Sink. The contents of some trace elements in each density fraction has been analyzed by ICAP. The analyzed data show that the alkaline-earth metals (Be, Sr, and Ba) have their special distributions in coal: Be and Sr may exist in the form of organic matter. Ba often has the highest content in the middle density fraction (1.4--1.5). The relative relationship between ash (or sulfur) and the trace element in a certain type of coal was obtained by using linear regression approach. Results show that there is no significant correlation between the contents of ash or sulfur and those of Be, Sr, and Ba. On the other hand, the linear regression was done among the trace elements of 17 types of coal. The results also show that there is no significant correlation between ash or sulfur and alkaline-earth metals.

  6. Theoretical study of the alkali and alkaline-earth monosulfides

    NASA Technical Reports Server (NTRS)

    Partridge, Harry; Langhoff, Stephen R.; Bauschlicher, Charles W., Jr.

    1988-01-01

    Ab initio calculations have been used to obtain accurate spectroscopic constants for the X2Pi and A2Sigma(+) states of the alkali sulfides and the X1Sigma(+), a3Pi, and A1Pi states of the alkaline-earth sulfides. In contrast to the alkali oxides, the alkali sulfides are found to have X2Pi ground states, due to the larger electrostatic interaction. Dissociation energies of 3.27 eV for BeS, 2.32 eV for MgS, 3.29 eV for CaS, and 3.41 eV for SrS have been obtained for the X1Sigma(+) states of the alkaline-earth sulfides, in good agreement with experimental results. Core correlation is shown to increase the Te values for the a3Pi and A1Pi states of MgS, CaS, and SrS.

  7. Steady-state superradiance with alkaline-earth-metal atoms

    SciTech Connect

    Meiser, D.; Holland, M. J.

    2010-03-15

    Alkaline-earth-metal-like atoms with ultranarrow transitions open the door to a new regime of cavity quantum electrodynamics. That regime is characterized by a critical photon number that is many orders of magnitude smaller than what can be achieved in conventional systems. We show that it is possible to achieve superradiance in steady state with such systems. We discuss the basic underlying mechanisms as well as the key experimental requirements.

  8. Molecular heterometallic hydride clusters composed of rare-earth and d-transition metals.

    PubMed

    Shima, Takanori; Luo, Yi; Stewart, Timothy; Bau, Robert; McIntyre, Garry J; Mason, Sax A; Hou, Zhaomin

    2011-09-18

    Heteromultimetallic hydride clusters containing both rare-earth and d-transition metals are of interest in terms of both their structure and reactivity. However, such heterometallic complexes have not yet been investigated to a great extent because of difficulties in their synthesis and structural characterization. Here, we report the synthesis, X-ray and neutron diffraction studies, and hydrogen addition and release properties of a family of rare-earth/d-transition-metal heteromultimetallic polyhydride complexes of the core structure type 'Ln(4)MH(n)' (Ln = Y, Dy, Ho; M = Mo, W; n = 9, 11, 13). Monitoring of hydrogen addition to a hydride cluster such as [{(C(5)Me(4)SiMe(3))Y}(4)(μ-H)(9)Mo(C(5)Me(5))] in a single-crystal to single-crystal process by X-ray diffraction has been achieved for the first time. Density functional theory studies reveal that the hydrogen addition process is cooperatively assisted by the Y/Mo heteromultimetallic sites, thus offering unprecedented insight into the hydrogen addition and release process of a metal hydride cluster.

  9. Proposal for Laser Cooling of Alkaline Earth Monoalkoxide Free Radicals

    NASA Astrophysics Data System (ADS)

    Baum, Louis; Kozyryev, Ivan; Matsuda, Kyle; Doyle, John M.

    2016-05-01

    Cold samples of polyatomic molecules will open new avenues in physics, chemistry, and quantum science. Non-diagonal Franck-Condon factors, technically challenging wavelengths, and the lack of strong electronic transitions inhibit direct laser cooling of nonlinear molecules. We identify a scheme for optical cycling in certain molecules with six or more atoms. Replacing hydrogen in alcohols with an alkaline earth metal (M) leads to alkaline earth monoalkoxide free radicals (MOR), which have favorable properties for laser cooling. M-O bond is very ionic, so the metal orbitals are slightly affected by the nature of R on the ligand. Diagonal Franck-Condon factors, laser accessible transitions, and a small hyperfine structure make MOR molecules suitable for laser cooling. We explore a scheme for optical cycling on the A - X transition of SrOCH3 . Molecules lost to dark vibrational states will be repumped on the B - X transition. Extension to larger species is possible through expansion of the R group since transitions involve the promotion of the metal-centered nonbonding valence electron. We will detail our estimations of the Franck-Condon factors, simulations of the cooling process and describe progress towards the Doppler cooling of MOR polyatomics.

  10. Recent advances in Rydberg physics using alkaline-earth atoms

    NASA Astrophysics Data System (ADS)

    Dunning, F. B.; Killian, T. C.; Yoshida, S.; Burgdörfer, J.

    2016-06-01

    In this brief review, the opportunities that the alkaline-earth elements offer for studying new aspects of Rydberg physics are discussed. For example, the bosonic alkaline-earth isotopes have zero nuclear spin which eliminates many of the complexities present in alkali Rydberg atoms, permitting simpler and more direct comparison between theory and experiment. The presence of two valence electrons allows the production of singlet and triplet Rydberg states that can exhibit a variety of attractive or repulsive interactions. The availability of weak intercombination lines is advantageous for laser cooling and for applications such as Rydberg dressing. Excitation of one electron to a Rydberg state leaves behind an optically active core ion allowing, for high-L states, the optical imaging of Rydberg atoms and their (spatial) manipulation using light scattering. The second valence electron offers the possibility of engineering long-lived doubly excited states such as planetary atoms. Recent advances in both theory and experiment are highlighted together with a number of possible directions for the future.

  11. Electronic, structural and transport properties of (almost) rare-earth-like actinide hydrides

    SciTech Connect

    Ward, J.W.; Cort, B.; Goldstone, J.A.; Lawson, A.C.; Cox, L.E. ); Haire, R.G. )

    1990-01-01

    By the virtue of broad-band, hybridized 5f-electron behavior, the hydride systems for Pa and U exhibit unique properties and structures, the actinide metal atoms existing in different states. A sudden change at Np to more rare-earth-like behavior implies a major change in electronic structure. There are both many parallels but also enigmas for the Np + H and Pu + H systems. Electrical resistivities are large and complex with temperature. Low-temperature structural transitions as studied by neutron diffraction help elucidate some of these effects. Phonon spectra are quite rare-earth-like, and XPS data imply a metal atom with mostly d-screened core levels. Then it is at americium, where fully localized and corelike 5f electrons are found, that we look finally for true rare-earth-like behavior, which should include a large drop in electrical resistivity. 33 refs., 7 figs., 1 tab.

  12. Enhanced Magnetic Trap Loading for Alkaline-Earth Atoms

    NASA Astrophysics Data System (ADS)

    Reschovsky, Benjamin J.; Barker, Daniel S.; Pisenti, Neal C.; Campbell, Gretchen K.

    2016-05-01

    We report on a technique to improve the continuous loading of atomic strontium into a magnetic trap from a Magneto-Optical Trap (MOT). This is achieved by adding a depumping laser addressing the 3P1 level. For the 3P1 -->3S1 (688-nm) transition in strontium, the depumping laser increases atom number in the magnetic trap and subsequent cooling stages by up to 65 % for the bosonic isotopes and up to 30 % for the fermionic isotope. We optimize this trap loading strategy with respect to the 688-nm laser detuning, intensity, and beam size. To understand the results, we develop a one-dimensional rate equation model of the system, which is in good agreement with the data. We discuss the use of other transitions in strontium for accelerated trap loading and the application of the technique to other alkaline-earth-like atoms.

  13. Structural diversity of alkaline-earth 2,5-thiophenedicarboxylates

    NASA Astrophysics Data System (ADS)

    Balendra; Ramanan, Arunachalam

    2017-03-01

    Exploration of the structural landscape of the system containing divalent alkaline-earth metal ion (Mg, Ca and Sr) with the rigid 2,5-thiophenedicarboxylic acid (TDC) under varying solvothermal condition (DMF, DMA and DEF) yielded five new crystals: [Mg(TDC) (DEF)2(H2O)1/2] (1), [Ca(TDC) (DMA)] (2), [Ca(TDC) (DMA) (H2O)] (3), [Sr(TDC) (DMA)] (4) and [Sr(TDC) (DMA) (H2O)] (5) and two known solids. Single crystal structures of all the solids are characteristic of extended coordination interaction between metal and carboxylate ions. While the smaller magnesium ion crystallized into a 2D coordination polymer, the larger calcium and strontium compounds resulted into the growth of 3D metal organic frameworks. All the solids show blue emission arising from intra ligand charge transfer.

  14. The significance of secondary interactions during alkaline earth-promoted dehydrogenation of dialkylamine-boranes.

    PubMed

    Bellham, Peter; Anker, Mathew D; Hill, Michael S; Kociok-Köhn, Gabriele; Mahon, Mary F

    2016-09-21

    a modified mechanism for group 2-mediated dimethylamine borane dehydrocoupling that is dependent on the intermediacy of key derivatives of the [NMe2·BH3](-) and [NMe2BH2NMe2BH3](-) anions but does not require the formation of high energy alkaline earth hydride intermediates. Although these results are specifically focussed on the applications of alkaline earth species, this mechanistic insight may also be relevant to other redox-inactive main group element-based systems and to our understanding of hydrogen evolution from saline derivatives of ammonia borane.

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

    PubMed

    Yang, Xiuli; Zhang, Junwei; Fang, Xihui

    2014-08-30

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

  16. Alkaline Earth Core Level Photoemission Spectroscopy of High-Temperature Superconductors

    NASA Technical Reports Server (NTRS)

    Vasquez, R.

    1993-01-01

    This paper examines photoemission measurements of the alkaline Earth core levels of high-temperature superconductors and related materials, models that seek to explain the large negative shifts observed relative to the corresponding alkaline Earth metals, and the effect of lattice site disorder on the core level spectra and the presence or absence of intrinsic surface peaks.

  17. Improvement of thermoelectric properties of alkaline-earth hexaborides

    SciTech Connect

    Takeda, Masatoshi . E-mail: takeda@mech.nagaokaut.ac.jp; Terui, Manabu; Takahashi, Norihito; Ueda, Noriyoshi

    2006-09-15

    Thermoelectric (TE) and transport properties of alkaline-earth hexaborides were examined to investigate the possibility of improvement in their TE performance. As carrier concentration increased, electrical conductivity increased and the absolute value of the Seebeck coefficient decreased monotonically, while carrier mobility was almost unchanged. These results suggest that the electrical properties of the hexaboride depend largely on carrier concentration. Thermal conductivity of the hexaboride was higher than 10 W/m K even at 1073 K, which is relatively high among TE materials. Alloys of CaB{sub 6} and SrB{sub 6} were prepared in order to reduce lattice thermal conductivity. Whereas the Seebeck coefficient and electrical conductivity of the alloys were intermediate between those of CaB{sub 6} and SrB{sub 6} single phases, the thermal conductivities of the alloys were lower than those of both single phases. The highest TE performance was obtained in the vicinity of Ca{sub 0.5}Sr{sub 0.5}B{sub 6}, indicating that alloying is effective in improving the performance. - Graphical abstract: Thermoelectric figure-of-merit, ZT, for (Ca,Sr)B{sub 6} alloys. The highest ZT value of 0.35 at 1073 K was obtained due to effective reduction of thermal conductivity by alloying.

  18. Effect of alkaline-earth ions on the dynamics of alkali ions in bismuthate glasses

    NASA Astrophysics Data System (ADS)

    Dutta, A.; Ghosh, A.

    2005-12-01

    The effect of alkaline earth ions on the dynamics of Li+ ions in bismuthate glasses has been studied in the temperature range 353-503K and in the frequency range 10Hz-2MHz . The dc conductivity increases and activation energy decreases with the increase of a particular alkaline earth content for the glasses with a fixed alkali content. The increased modification of the network due to the increase in alkaline earth content in the compositions is responsible for the increasing conductivity. Also the compositions with smaller alkaline earth ions were found to exhibit higher conductivity. Although the conductivity increases with the decrease of ionic radii of alkaline earth ions, the activation energy shows a maximum for the Sr ion. The electric modulus and the conductivity formalisms have been employed to study the relaxation dynamics of charge carriers in these glasses. The alkali ions were observed to change their dynamics with the change of the alkaline earth ions. The same anomalous trend for activation energy for the conductivity relaxation frequency and the hopping frequency was also observed for glasses containing SrO. It was also observed that the mobile lithium ion concentrations are independent of nature of alkaline earth ions in these glasses.

  19. Physical and electrochemical properties of alkaline earth doped, rare earth vanadates

    SciTech Connect

    Adijanto, Lawrence; Balaji Padmanabhan, Venu; Holmes, Kevin J.; Gorte, Raymond J.; Vohs, John M.

    2012-06-15

    The effect of partial substitution of alkaline earth (AE) ions, Sr{sup 2+} and Ca{sup 2+}, for the rare earth (RE) ions, La{sup 3+}, Ce{sup 3+}, Pr{sup 3+}, and Sm{sup 3+}, on the physical properties of REVO{sub 4} compounds were investigated. The use of the Pechini method to synthesize the vanadates allowed for high levels of AE substitution to be obtained. Coulometric titration was used to measure redox isotherms for these materials and showed that the addition of the AE ions increased both reducibility and electronic conductivity under typical solid oxide fuel cell (SOFC) anode conditions, through the formation of compounds with mixed vanadium valence. In spite of their high electronic conductivity, REVO{sub 4}-yttira stabilized zirconia (YSZ) composite anodes exhibited only modest performance when used in SOFCs operating with H{sub 2} fuel at 973 K due to their low catalytic activity. High performance was obtained, however, after the addition of a small amount of catalytically active Pd to the anode. - Graphical abstract: Coulometric titration isotherms for ({open_square}) LaVO{sub 4}, ( White-Circle ) PrVO{sub 4}, ( Lozenge ) CeVO{sub 4}, ( Black-Up-Pointing-Triangle ) Ce{sub 0.7}Sr{sub 0.3}VO{sub 3.85}, and ( Black-Square ) Ce{sub 0.7}Ca{sub 0.3}VO{sub 3.85}, at 973 K. Highlights: Black-Right-Pointing-Pointer Infiltration procedures were used to prepare SOFC anodes from various vanadates. Black-Right-Pointing-Pointer Doping of Alkaline Earth to Rare Earth Vanadates showed to improve conductivity and chemical stability. Black-Right-Pointing-Pointer Alkaline Earth Doped Rare Earth Vanadates-YSZ composites showed conductivities as high as 5 S cm{sup -1} at 973 K. Black-Right-Pointing-Pointer As with other ceramic anodes, the addition of a catalyst was required to achieve low anode impedance.

  20. Physical and electrochemical properties of alkaline earth doped, rare earth vanadates

    NASA Astrophysics Data System (ADS)

    Adijanto, Lawrence; Balaji Padmanabhan, Venu; Holmes, Kevin J.; Gorte, Raymond J.; Vohs, John M.

    2012-06-01

    The effect of partial substitution of alkaline earth (AE) ions, Sr2+ and Ca2+, for the rare earth (RE) ions, La3+, Ce3+, Pr3+, and Sm3+, on the physical properties of REVO4 compounds were investigated. The use of the Pechini method to synthesize the vanadates allowed for high levels of AE substitution to be obtained. Coulometric titration was used to measure redox isotherms for these materials and showed that the addition of the AE ions increased both reducibility and electronic conductivity under typical solid oxide fuel cell (SOFC) anode conditions, through the formation of compounds with mixed vanadium valence. In spite of their high electronic conductivity, REVO4-yttira stabilized zirconia (YSZ) composite anodes exhibited only modest performance when used in SOFCs operating with H2 fuel at 973 K due to their low catalytic activity. High performance was obtained, however, after the addition of a small amount of catalytically active Pd to the anode.

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

    SciTech Connect

    Provo, James L.

    2015-07-15

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

  2. Release characteristics of alkali and alkaline earth metallic species during biomass pyrolysis and steam gasification process.

    PubMed

    Long, Jiang; Song, Hu; Jun, Xiang; Sheng, Su; Lun-Shi, Sun; Kai, Xu; Yao, Yao

    2012-07-01

    Investigating the release characteristics of alkali and alkaline earth metallic species (AAEMs) is of potential interest because of AAEM's possible useful service as catalysts in biomass thermal conversion. In this study, three kinds of typical Chinese biomass were selected to pyrolyse and their chars were subsequently steam gasified in a designed quartz fixed-bed reactor to investigate the release characteristics of alkali and alkaline earth metallic species (AAEMs). The results indicate that 53-76% of alkali metal and 27-40% of alkaline earth metal release in pyrolysis process, as well as 12-34% of alkali metal and 12-16% of alkaline earth metal evaporate in char gasification process, and temperature is not the only factor to impact AAEMs emission. The releasing characteristics of AAEMs during pyrolysis and char gasification process of three kinds of biomass were discussed in this paper.

  3. More arrows in the quiver: new pathways and old problems with heavy alkaline earth metal diphenylmethanides.

    PubMed

    Alexander, Jacob S; Ruhlandt-Senge, Karin

    2004-03-05

    Progress in the field of sigma-bonded alkaline earth organometallics has been handicapped by numerous complications, such as high reactivity, low solubility, and the limited availability of suitable starting materials. Here we present two synthetic methods, hydrocarbon elimination and desilylation, as alternative routes into this chemistry. A novel barium diphenylmethanide was prepared using these routes delineating that both methods provide a powerful, versatile synthetic access route to an extended library of organometallic alkaline earth derivatives.

  4. Process for preparing higher oxides of the alkali and alkaline earth metals

    NASA Technical Reports Server (NTRS)

    Sadhukhan, P.; Bell, A. (Inventor)

    1978-01-01

    High purity inorganic higher oxides of the alkali and alkaline earth metals are prepared by subjecting the hydroxide of the alkali and alkaline earth metal to a radio frequency discharge sustained in oxygen. The process is particulary adaptable to the production of high purity potassium superoxide by subjecting potassium hydroxide to glow discharge sustained in oxygen under the pressure of about 0.75 to 1.00 torr.

  5. Structure and ionic diffusion of alkaline-earth ions in mixed cation glasses

    SciTech Connect

    Konstantinou, Konstantinos; Sushko, Petr; Duffy, Dorothy M.

    2015-08-15

    A series of mixed cation silicate glasses of the composition A2O – 2MO – 4SiO2, with A=Li,Na,K and M=Ca,Sr,Ba has been investigated by means of molecular dynamics simulations in order to understand the effect of the nature of the cations on the mobility of the alkaline-earth ions within the glass network. The size of the alkaline-earth cation was found to affect the inter-atomic distances, the coordination number distributions and the bond angle distributions , whereas the medium-range order was almost unaffected by the type of the cation. All the alkaline-earth cations contribute to lower vibrational frequencies but it is observed that that there is a shift to smaller frequencies and the vibrational density of states distribution gets narrower as the size of the alkaline-earth increases. The results from our modeling for the ionic diffusion of the alkaline-earth cations are in a qualitative agreement with the experimental observations in that there is a distinct correlation between the activation energy for diffusion of alkaline earth-ions and the cation radii ratio. An asymmetrical linear behavior in the diffusion activation energy with increasing size difference is observed. The results can be described on the basis of a theoretical model that relates the diffusion activation energy to the electrostatic interactions of the cations with the oxygens and the elastic deformation of the silicate network.

  6. High H- ionic conductivity in barium hydride

    NASA Astrophysics Data System (ADS)

    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.

  7. [Broad excitation band alkaline-earth silicate luminescent materials activated by rare earth and its applications].

    PubMed

    Xia, Wei; Lei, Ming-Kai; Luo, Xi-Xian; Xiao, Zhi-Guo

    2008-01-01

    Series of novel broad excitation band phosphors M2 MgSis O7 : Eu, Dy(M = Ca, Sr) were prepared by a high temperature solid-state reaction method. The crystal structure of compound was characterized. And the effects of part substitution of alkaline-earth on crystal structure, photoluminescence spectra and luminescence properties were also investigated. It is found that the excitation band of silicate luminescent materials extend to visible region and they exhibit yellow, green and blue long after-glow luminescence after excited by ultraviolet or visible light. Ca MgSi O7 : Eu, Dy luminescent materials can be excited effectively under the 450-480 nm range and exhibit a strong emission at 536 nm, nicely combining with blue light emitted by InGaN chips to produce white light. This promises the silicate luminescent materials a potential yellow phosphor for white LED.

  8. Dynamics of dipolar defects in rare earth-doped alkaline-earth fluoride crystals

    NASA Astrophysics Data System (ADS)

    Charnock, Forrest Taylor

    Alkaline-earth fluoride crystals such as SrF2 provide an excellent sample material for investigating the physics of point defects in crystal lattices. High quality crystals are easily grown, and they readily accept many dopant ions into the lattice, particularly rare earth ions. Rare earth dopant ions (typically trivalent) occupy substitutional sites in the lattice by replacing a Sr2+ ion. Due to the extra charge of the rare earth ion, charge compensation is often provided by an extra fluoride ion (F--) located in a nearby interstitial position. If located in the nearest-neighbor (nn) interstitial position, it forms a defect with C4n symmetry; if located in the next-nearest-neighbor (nnn) intersitial position, it forms a defect with C3n symmetry. Given sufficient thermal energy, this interstitial F ion can move to adjacent interstitial sites and hence reorient the defect. The rate w at which the ion moves from one interstitial site to another is well described by a simple Arrhenius expression: w=n0e-E/kT , where n0 is the attack frequency of the F-- and E is the activation energy. This motion can profoundly affect both the electronic polarizability of the material and the polarization of light emitted or absorbed by the rare earth ion. This thesis describes the normal mode motion of interstitial ions which may occupy either nn or nnn interstitial sites. Using electron paramagnetic resonance (EPR), I observed the relative populations of nn and nnn defects in SrF2 doped with Gd3+ as a function of temperature. These measurements show that dipolar reorientation of the nnn F occurs through the nn interstitial position. Not all interstitial F-- motion is thermally driven. Fluorescence depolarization measurements of SrF2:Pr3+ indicate that optically stimulating a Pr3+ may induce interstitial motion of a nn F--. Such motion was confirmed by showing that nn defects in SrF2:Pr3+ may be polarized at very low temperatures when the sample is illuminated with resonant light. I

  9. Rare-earth-doped bifunctional alkaline-earth metal fluoride nanocrystals via a facile microwave-assisted process.

    PubMed

    Pang, Min; Liu, Dapeng; Lei, Yongqian; Song, Shuyan; Feng, Jing; Fan, Weiqiang; Zhang, Hongjie

    2011-06-20

    Rare-earth-doped magnetic-optic bifunctional alkaline-earth metal fluoride nanocrystals have been successfully synthesized via a facile microwave-assisted process. The as-prepared nanocrystals were monodisperse and could form stable colloidal solutions in polar solvents, such as water and ethanol. They show bright-green fluorescence emisson. Furthermore, Gd(3+)-doped ones exhibit paramagnetic behavior at room temperature and superparamagnetic behavior at 2 K.

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

    PubMed

    Harder, Sjoerd

    2012-11-25

    Within the general area of early main group metal chemistry, the controlled synthesis of well-defined metal hydride complexes is a rapidly developing research field. As group 1 and 2 metal complexes are generally highly dynamic and lattice energies for their [MH](∞) and [MH(2)](∞) salts are high, the synthesis of well-defined soluble hydride complexes is an obvious challenge. Access to molecular early main group metal hydrides, however, is rewarding: these hydrocarbon-soluble metal hydrides are highly reactive, have found use in early main group metal catalysis and are potentially also valuable molecular model systems for polar metal hydrides as a hydrogen storage material. The article focusses specifically on alkali and alkaline-earth metal hydride complexes and discusses the synthetic challenge, molecular structures, reactivity and applications.

  11. Charge-separated and molecular heterobimetallic rare earth-rare earth and alkaline earth-rare earth aryloxo complexes featuring intramolecular metal-pi-arene interactions.

    PubMed

    Deacon, Glen B; Junk, Peter C; Moxey, Graeme J; Ruhlandt-Senge, Karin; St Prix, Courtney; Zuniga, Maria F

    2009-01-01

    Treatment of a rare earth metal (Ln) and a potential divalent rare earth metal (Ln') or an alkaline earth metal (Ae) with 2,6-diphenylphenol (HOdpp) at elevated temperatures (200-250 degrees C) afforded heterobimetallic aryloxo complexes, which were structurally characterised. A charge-separated species [(Ln'/Ae)(2)(Odpp)(3)][Ln(Odpp)(4)] was obtained for a range of metals, demonstrating the similarities between the chemistry of the divalent rare earth metals and the alkaline earth metals. The [(Ln'/Ae)(2)(Odpp)(3)](+) cation in the heterobimetallic structures is unusual in that it consists solely of bridging aryloxide ligands. A molecular heterobimetallic species [AeEu(Odpp)(4)] (Ae = Ca, Sr, Ba) was obtained by treating an alkaline earth metal and Eu metal with HOdpp at elevated temperatures. Similarly, [BaSr(Odpp)(4)] was prepared by treating Ba metal and Sr metal with HOdpp. Treatment of [Ba(2)(Odpp)(4)] with [Mg(Odpp)(2)(thf)(2)] in toluene afforded [Ba(2)(Odpp)(3)][Mg(Odpp)(3)(thf)]. Analogous solution-based syntheses were not possible for [(Ln'/Ae)(2)(Odpp)(3)][Ln(Odpp)(4)] complexes, for which the free-metal route was essential. As a result of the absence of additional donor ligands, the crystal structures of the heterobimetallic complexes feature extensive pi-Ph-metal interactions involving the pendant phenyl groups of the Odpp ligands, thus enabling the large electropositive metal atoms to attain coordination saturation. The charge-separated heterobimetallic species were purified by extraction with toluene/thf mixtures at ambient temperature (Ba-containing compounds) or by extraction with toluene under pressure above the boiling point of the solvent (other products). In donor solvents, heterobimetallic complexes other than those containing barium were found to fragment into homometallic species.

  12. Depolarizing collisions with hydrogen: Neutral and singly ionized alkaline earths

    SciTech Connect

    Manso Sainz, Rafael; Ramos, Andrés Asensio; Bueno, Javier Trujillo; Aguado, Alfredo

    2014-06-20

    Depolarizing collisions are elastic or quasielastic collisions that equalize the populations and destroy the coherence between the magnetic sublevels of atomic levels. In astrophysical plasmas, the main depolarizing collider is neutral hydrogen. We consider depolarizing rates on the lowest levels of neutral and singly ionized alkali earths Mg I, Sr I, Ba I, Mg II, Ca II, and Ba II, due to collisions with H°. We compute ab initio potential curves of the atom-H° system and solve the quantum mechanical dynamics. From the scattering amplitudes, we calculate the depolarizing rates for Maxwellian distributions of colliders at temperatures T ≤ 10,000 K. A comparative analysis of our results and previous calculations in the literature is completed. We discuss the effect of these rates on the formation of scattering polarization patterns of resonant lines of alkali earths in the solar atmosphere, and their effect on Hanle effect diagnostics of solar magnetic fields.

  13. IUPAC-NIST Solubility Data Series. 79. Alkali and Alkaline Earth Metal Pseudohalides

    NASA Astrophysics Data System (ADS)

    Hála, Jiri

    2004-03-01

    This volume presents solubility data of azides, cyanides, cyanates, and thiocyanates of alkali metals, alkaline earth metals, and ammonium. Covered are binary and ternary systems in all solvents. No solubility data have been found for some of the compounds of alkali metals, alkaline metals, and ammonium. These include beryllium and magnesium azides, lithium, rubidium cesium, ammonium, and alkaline earth cyanates and cyanides, and beryllium thiocyanate. Likewise, no solubility data seem to exist for selenocyanates of the mentioned metals and ammonium. The literature has been covered up to the middle of 2001, and there was a great effort to have the literature survey as complete as possible. The few documents which remained unavailable to the editor, and could not be included in the volume, are listed in the Appendix. For some compounds it was not possible to show the Chemical Abstracts registry numbers since these have not been assigned. For this reason, the registry number index is incomplete.

  14. Systematic studies of the mass spectrometric properties of alkaline earth metal cationized amino acids and peptides

    NASA Astrophysics Data System (ADS)

    Küjckelmann, Ulrich; Müller, Dietrich; Weber, Carsten

    1997-07-01

    The results of a systematic study of the gas phase interactions of α-amino acids and peptides (4-15 amino acids) with alkaline earth metals, observed with mass spectrometric techniques, are presented. Furthermore, a model for the cationization with calcium at the C-terminal amino acid arginine in rotaviral polypeptides is presented.

  15. Recent developments in the field of organic heterobimetallic compounds of the alkaline-earth metals.

    PubMed

    Westerhausen, Matthias

    2006-10-28

    Heterobimetallic compounds of the alkaline-earth metals show a wide structural variety with strongly differing reactivity patterns. The combination of magnesium and alkali metal amides yields cyclic molecules with an extreme high reactivity which often are considered as "inverse crowns" with the metal atoms as coordination sites for Lewis bases. In other metallates of the alkaline-earth metals an activation of alkyl groups succeeds. In alkaline-earth metal zincates an inverse coordination of the type M(2)[(mu-R)(2)ZnR](2) is observed and the alkyl groups are in bridging positions between zinc and the s-block metals thus forming a very reactive M-C-Zn three-center-two-electron bond. Furthermore, the metals of the carbon group form alkaline-earth metal-silicon, -germanium and -tin bonds or, in the presence of very strong Lewis bases, even solvent-separated ion pairs. For electronegative substituents at tin an inverse coordination mode such as M[(mu-R)(2)SnR](2) is observed.

  16. Homoleptic alkaline earth metal bis(trifluoromethanesulfonyl)imide complex compounds obtained from an ionic liquid.

    PubMed

    Babai, Arash; Mudring, Anja-Verena

    2006-04-17

    The first homoleptic alkaline earth bis(trifluoromethanesulfonyl)imide (Tf2N) complexes [mppyr]2[Ca(Tf2N)4], [mppyr]2[Sr(Tf2N)4], and [mppyr][Ba(Tf2N)3] were crystallized from a solution of the respective alkaline earth bis(trifluoromethanesulfonyl)imide and the ionic liquid [mppyr][Tf2N] (mppyr = 1,1-N-methyl-N-propylpyrrolidinium). In the calcium and strontium compounds, the alkaline earth metal (AE) is coordinated by four bidentately chelating Tf2N ligands to form isolated (distorted) square antiprismatic [AE(Tf2N)4]2- complexes which are separated by N-methyl-N-propylpyrrolidinium cations. In contrast, the barium compound, [mppyr][Ba(Tf2N)3], forms an extended structure. Here the alkaline earth cation is surrounded by six oxygen atoms belonging to three Tf2N- anions which coordinate in a bidentate chelating fashion. Three further oxygen atoms of the same ligands are linking the Ba2+ cations to infinite (infinity)(1)[Ba(Tf2N)3] chains.

  17. Coordination Chemistry of Alkali and Alkaline-Earth Cations with Macrocyclic Ligands.

    ERIC Educational Resources Information Center

    Dietrich, Bernard

    1985-01-01

    Discusses: (l) alkali and alkaline-earth cations in biology (considering naturally occurring lonophores, their X-ray structures, and physiochemical studies); (2) synthetic complexing agents for groups IA and IIA; and (3) ion transport across membranes (examining neutral macrobicyclic ligands as metal cation carriers, transport by anionic carriers,…

  18. Ca12InC13-x and Ba12InC18H4: alkaline-earth indium allenylides synthesized in AE/Li flux (AE = Ca, Ba).

    PubMed

    Blankenship, Trevor V; Dickman, Matthew J; van de Burgt, Lambertus J; Latturner, Susan E

    2015-02-02

    Two new complex main-group metal carbides were synthesized from reactions of indium, carbon, and a metal hydride in metal flux mixtures of an alkaline earth (AE = Ca, Ba) and lithium. Ca(12)InC(13-x) and Ba(12)InC(18)H(4) both crystallize in cubic space group Im3̅ [a = 9.6055(8) and 11.1447(7) Å, respectively]. Their related structures are both built on a body-centered-cubic array of icosahedral clusters comprised of an indium atom and 12 surrounding alkaline-earth cations; these clusters are connected by bridging monatomic anions (either H(-) or C(4-)) and allenylide anions, C(3)(4-). The allenylide anions were characterized by Raman spectroscopy and hydrolysis studies. Density of states and crystal orbital Hamilton population calculations confirm that both compounds are metallic.

  19. Metal Based Synthetic Strategies and the Examination of Structure Determining Factors in Alkaline Earth Metal Compounds

    NASA Astrophysics Data System (ADS)

    Takahashi, Yuriko

    Last decades have witnessed a large expansion of the organometallic heavier alkaline earth metal species. However, continued growth of this promising area of chemistry has been slowed by severe restrictions and limitations in viable synthetic methodologies leading to difficulties in preparing and characterizing the target compounds. There is clearly a need for the further development of synthetic methodologies and detailed structure function analysis that will promote the further advancement of organoalkaline earth metal chemistry in applications as diverse as materials chemistry and catalysis. This thesis work greatly extends the synthetic options currently available towards organoalkaline earth metal species by introducing redox transmetallation protolysis (RTP), a reaction based on the readily available Ph3Bi as a non-toxic transmetallation agent. Based on a straightforward one-pot procedure and work-up, Ph3Bi based RTP presents a powerful synthetic alternative for the facile preparation of a large variety of heavy alkaline earth metal compounds. The second part of the thesis explores the effect of secondary non covalent interactions on the coordination chemistry as well as thermal properties of a series of novel alkali, alkaline earth, rare earth as well as heterobimetallic alkali/alkaline earth fluoroalkoxides. These compounds showcase the significance of non-covalent M···F-C and agostic interactions on metal stabilization and structural features, providing critical input on ligand design for the design of advanced metal organic vapor deposition (MOCVD) precursor materials. This work also showcases the impact of M···F-C interactions over M---co-ligand coordination, a critical precursor design element as well.

  20. Carbonatite and alkaline intrusion-related rare earth element deposits–A deposit model

    USGS Publications Warehouse

    Verplanck, Philip L.; Van Gosen, Bradley S.

    2011-01-01

    The rare earth elements are not as rare in nature as their name implies, but economic deposits with these elements are not common and few deposits have been large producers. In the past 25 years, demand for rare earth elements has increased dramatically because of their wide and diverse use in high-technology applications. Yet, presently the global production and supply of rare earth elements come from only a few sources. China produces more than 95 percent of the world's supply of rare earth elements. Because of China's decision to restrict exports of these elements, the price of rare earth elements has increased and industrial countries are concerned about supply shortages. As a result, understanding the distribution and origin of rare earth elements deposits, and identifying and quantifying our nation's rare earth elements resources have become priorities. Carbonatite and alkaline intrusive complexes, as well as their weathering products, are the primary sources of rare earth elements. The general mineral deposit model summarized here is part of an effort by the U.S. Geological Survey's Mineral Resources Program to update existing models and develop new descriptive mineral deposit models to supplement previously published models for use in mineral-resource and mineral-environmental assessments. Carbonatite and alkaline intrusion-related REE deposits are discussed together because of their spatial association, common enrichment in incompatible elements, and similarities in genesis. A wide variety of commodities have been exploited from carbonatites and alkaline igneous rocks, such as rare earth elements, niobium, phosphate, titanium, vermiculite, barite, fluorite, copper, calcite, and zirconium. Other enrichments include manganese, strontium, tantalum, thorium, vanadium, and uranium.

  1. Ab initio study of the alkali and alkaline-earth monohydroxides

    NASA Technical Reports Server (NTRS)

    Bauschlicher, C. W., Jr.; Langhoff, S. R.; Partridge, H.

    1986-01-01

    A systematic study of the structures and dissociation energies of all the alkali and alkaline-earth monohydroxides is conducted. A theoretical model for determining accurate dissociation energies of ionic molecules is discussed. The obtained theoretical structures and dissociation energies of the alkali and alkaline-earth monohydroxides, respectively, are compared with experimental data. It is found that the theoretical studies of the bending potentials of BeOH, MgOH, and CaOH reveal the different admixture of covalent character in these systems. The BeOH molecule with the largest degree of covalent character is found to be bent (theta equals 147 deg). The MgOH is also linear. The theoretical dissociation energies for the alkali and akaline-earth hydroxides are thought to be accurate to 0.1 eV.

  2. Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

    DOEpatents

    Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

    1995-01-01

    The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

  3. Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

    DOEpatents

    Tierney, J.W.; Wender, I.; Palekar, V.M.

    1995-01-31

    The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100--160 C and the pressure range of 40--65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H[sub 2]/CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

  4. Research into processes of production of hydrides of materials containing rare-earth metals and their corrosion

    NASA Astrophysics Data System (ADS)

    Sofronov, V. L.; Kartashov, E. Y.; Molokov, P. B.; Zhiganov, A. N.; Kalaev, M. E.

    2017-01-01

    Production of permanent magnets on basis of rare earth elements (REE) is implemented by means of powder metallurgy, therefore a technologically important operation is the multistage mechanical crushing of materials to the extent of domains. The promising technique of crushing of magnetic materials is their consistent hydrogenation-dehydrogenation that allows obtaining nano-dispersed powders which are stable enough in air. Hydrogenation apparatuses, as opposed to conventional grinding machines, do not comprise motion works and their producing capacity is much higher. Hydrogenation process does not require any additional preparation of materials and it excludes undermilling and overmilling as well as material oxidation. The paper presents the results of investigation on the temperature effect on the hydrogenation process of Nd-Fe alloys. The study results on the corrosion stability of ligature hydrides under various conditions are also given. Kinetic parameters of the hydrogenation process of ligatures are determined. The phase composition of corrosion products is detected. Guidelines on hydride powder storage are given.

  5. Ab initio calculations on the positive ions of the alkaline-earth oxides, fluorides, and hydroxides

    NASA Technical Reports Server (NTRS)

    Partridge, H.; Langhoff, S. R.; Bauschlicher, C. W., Jr.

    1986-01-01

    Theoretical dissociation energies are presented for the alkaline-earth fluoride, hydroxide, and oxide positive ions that are considered to be accurate to 0.1-0.2 eV. The r(e) for the positive ions are found to be consistently shorter than the corresponding neutrals by 0.07 + or -0.02 A. The bonding in the ground states is demonstrated to be of predominantly M + 2 X - character. The a 3 Pi and A 1 Pi are found to lie considerably above the X 1 Sigma + ground states of the alkaline-earth fluoride and hydroxide positive ions. The overall agreement of the theoretical ionization potentials with the available experimental appearance potentials is satisfactory; these values should represent the most accurate and consistent set available.

  6. Effects of inherent alkali and alkaline earth metallic species on biomass pyrolysis at different temperatures.

    PubMed

    Hu, Song; Jiang, Long; Wang, Yi; Su, Sheng; Sun, Lushi; Xu, Boyang; He, Limo; Xiang, Jun

    2015-09-01

    This work aimed to investigate effects of inherent alkali and alkaline earth metallic species (AAEMs) on biomass pyrolysis at different temperatures. The yield of CO, H2 and C2H4 was increased and that of CO2 was suppressed with increasing temperature. Increasing temperature could also promote depolymerization and aromatization reactions of active tars, forming heavier polycyclic aromatic hydrocarbons, leading to decrease of tar yields and species diversity. Diverse performance of inherent AAEMs at different temperatures significantly affected the distribution of pyrolysis products. The presence of inherent AAEMs promoted water-gas shift reaction, and enhanced the yield of H2 and CO2. Additionally, inherent AAEMs not only promoted breakage and decarboxylation/decarbonylation reaction of thermally labile hetero atoms of the tar but also enhanced thermal decomposing of heavier aromatics. Inherent AAEMs could also significantly enhance the decomposition of levoglucosan, and alkaline earth metals showed greater effect than alkali metals.

  7. IUPAC-NIST Solubility Data Series. 95. Alkaline Earth Carbonates in Aqueous Systems. Part 2. Ca

    SciTech Connect

    De Visscher, Alex; Vanderdeelen, Jan

    2012-06-15

    The alkaline earth carbonates are an important class of minerals. This article is part of a volume in the IUPAC-NIST Solubility Data Series that compiles and critically evaluates solubility data of the alkaline earth carbonates in water and in simple aqueous electrolyte solutions. Part 1 outlined the procedure adopted in this volume, and presented the beryllium and magnesium carbonates. Part 2, the current paper, compiles and critically evaluates the solubility data of calcium carbonate. The chemical forms included are the anhydrous CaCO{sub 3} types calcite, aragonite, and vaterite, the monohydrate monohydrocalcite (CaCO{sub 3}{center_dot} H{sub 2}O), the hexahydrate ikaite (CaCO{sub 3}{center_dot}6H{sub 2}O), and an amorphous form. The data were analyzed with two model variants, and thermodynamic data of each form consistent with each of the models and with the CODATA key values for thermodynamics are presented.

  8. Advances in the growth of alkaline-Earth halide single crystals for scintillator detectors

    NASA Astrophysics Data System (ADS)

    Boatner, L. A.; Ramey, J. O.; Kolopus, J. A.; Neal, J. S.; Cherepy, N. J.; Beck, P. R.; Payne, S. A.; Burger, A.; Rowe, E.; Bhattacharya, P.

    2014-09-01

    Alkaline-earth scintillators such as strontium iodide and other alkaline-earth halides activated with divalent europium represent some of the most efficient and highest energy resolution scintillators for use as gamma-ray detectors in a wide range of applications. These applications include the areas of nuclear nonproliferation, homeland security, the detection of undeclared nuclear material, nuclear physics and materials science, medical diagnostics, space physics, high energy physics, and radiation monitoring systems for first responders, police, and fire/rescue personnel. Recent advances in the growth of large single crystals of these scintillator materials hold the promise of higher crystal yields and significantly lower detector production costs. In the present work, we describe new processing protocols that, when combined with our molten salt filtration methods, have led to advances in achieving a significant reduction of cracking effects during the growth of single crystals of SrI2:Eu2+. In particular, we have found that extended pumping on the molten crystalgrowth charge under vacuum for time periods extending up to 48 hours is generally beneficial in compensating for variations in the alkaline-earth halide purity and stoichiometry of the materials as initially supplied by commercial sources. These melt-pumping and processing techniques are now being applied to the purification of CaI2:Eu2+ and some mixed-anion europium-doped alkaline-earth halides prior to single-crystal growth by means of the vertical Bridgman technique. The results of initial studies of the effects of aliovalent doping of SrI2:Eu2+ on the scintillation characteristics of this material are also described.

  9. Surface energetics of alkaline-earth metal oxides: Trends in stability and adsorption of small molecules

    NASA Astrophysics Data System (ADS)

    Bajdich, Michal; Nørskov, Jens K.; Vojvodic, Aleksandra

    2015-04-01

    We present a systematic theoretical investigation of the surface properties, stability, and reactivity of rocksalt type alkaline-earth metal oxides including MgO, CaO, SrO, and BaO. The accuracy of commonly used exchange-correlation density functionals (LDA, PBE, RPBE, PBEsol, BEEF-vdW, and hybrid HSE) and random-phase approximation (RPA) is evaluated and compared to existing experimental values. Calculated surface energies of the four most stable surface facets under vacuum conditions, the (100) surface, the metal and oxygen terminated octopolar (111), and the (110) surfaces, exhibit a monotonic increase in stability from MgO to BaO. On the MgO(100) surface, adsorption of CO, NO, and CH4 is characterized by physisorption while H2O chemisorbs, which is in agreement with experimental findings. We further use the on-top metal adsorption of CO and NO molecules to map out the surface energetics of each alkaline-earth metal oxide surface. The considered functionals all qualitatively predict similar adsorption energy trends. The ordering between the adsorption energies on different surface facets can be attributed to differences in the local geometrical surface structure and the electronic structure of the metal constituent of the alkaline-earth metal oxide. The striking observation that CO adsorption strength is weaker than NO adsorption on the (100) terraces as the period of the alkaline-earth metal in the oxide increases is analyzed in detail in terms of charge redistribution within the σ and π channels of adsorbates. Finally, we also present oxygen adsorption and oxygen vacancy formation energies in these oxide systems.

  10. Properties of the triplet metastable states of the alkaline-earth-metal atoms

    SciTech Connect

    Mitroy, J.; Bromley, M.W.J.

    2004-11-01

    The static and dynamic properties of the alkaline-earth-metal atoms in their metastable state are computed in a configuration interaction approach with a semiempirical model potential for the core. Among the properties determined are the scalar and tensor polarizabilities, the quadrupole moment, some of the oscillator strengths, and the dispersion coefficients of the van der Waals interaction. A simple method for including the effect of the core on the dispersion parameters is described.

  11. Advances in the growth of alkaline-earth halide single crystals for scintillator detectors

    SciTech Connect

    Boatner, Lynn A; Ramey, Joanne Oxendine; Kolopus, James A; Neal, John S; Cherepy, Nerine; Payne, Stephen A.; Beck, P; Burger, Arnold; Rowe, E; Bhattacharya, P.

    2014-01-01

    Alkaline-earth scintillators such as strontium iodide and other alkaline-earth halides activated with divalent europium represent some of the most efficient and highest energy resolution scintillators for use as gamma-ray detectors in a wide range of applications. These applications include the areas of nuclear nonproliferation, homeland security, the detection of undeclared nuclear material, nuclear physics and materials science, medical diagnostics, space physics, high energy physics, and radiation monitoring systems for first responders, police, and fire/rescue personnel. Recent advances in the growth of large single crystals of these scintillator materials hold the promise of higher crystal yields and significantly lower detector production costs. In the present work, we describe new processing protocols that, when combined with our molten salt filtration methods, have led to advances in achieving a significant reduction of cracking effects during the growth of single crystals of SrI2:Eu2+. In particular, we have found that extended pumping on the molten crystal-growth charge under vacuum for time periods extending up to 48 hours is generally beneficial in compensating for variations in the alkaline-earth halide purity and stoichiometry of the materials as initially supplied by commercial sources. These melt-pumping and processing techniques are now being applied to the purification of CaI2:Eu2+ and some mixed-anion europium-doped alkaline-earth halides prior to single-crystal growth by means of the vertical Bridgman technique. The results of initial studies of the effects of aliovalent doping of SrI2:Eu2+ on the scintillation characteristics of this material are also described.

  12. Energetics of alkali and alkaline earth ion-exchanged zeolite A

    DOE PAGES

    Sun, Hui; Wu, Di; Liu, Kefeng; ...

    2016-06-30

    Alkali and alkaline earth ion-exchanged zeolite A samples were synthesized in aqueous exchange media. They were thoroughly studied by powder X-ray diffraction (XRD), electron microprobe (EMPA), thermogravimetric analysis and differential scanning calorimetry (TG-DSC), and high temperature oxide melt solution calorimetry. The hydration energetics and enthalpies of formation of these zeolite A materials from constituent oxides were determined. Specifically, the hydration level of zeolite A has a linear dependence on the average ionic potential (Z/r) of the cation, from 0.894 (Rb-A) to 1.317 per TO2 (Mg-A). The formation enthalpies from oxides (25 °C) range from –93.71 ± 1.77 (K-A) to –48.02more » ± 1.85 kJ/mol per TO2 (Li-A) for hydrated alkali ion-exchanged zeolite A, and from –47.99 ± 1.20 (Ba-A) to –26.41 ± 1.71 kJ/mol per TO2 (Mg-A) for hydrated alkaline earth ion-exchanged zeolite A. As a result, the formation enthalpy from oxides generally becomes less exothermic as Z/r increases, but a distinct difference in slope is observed between the alkali and the alkaline earth series.« less

  13. Energetics of alkali and alkaline earth ion-exchanged zeolite A

    SciTech Connect

    Sun, Hui; Wu, Di; Liu, Kefeng; Guo, Xiaofeng; Navrotsky, Alexandra

    2016-06-30

    Alkali and alkaline earth ion-exchanged zeolite A samples were synthesized in aqueous exchange media. They were thoroughly studied by powder X-ray diffraction (XRD), electron microprobe (EMPA), thermogravimetric analysis and differential scanning calorimetry (TG-DSC), and high temperature oxide melt solution calorimetry. The hydration energetics and enthalpies of formation of these zeolite A materials from constituent oxides were determined. Specifically, the hydration level of zeolite A has a linear dependence on the average ionic potential (Z/r) of the cation, from 0.894 (Rb-A) to 1.317 per TO2 (Mg-A). The formation enthalpies from oxides (25 °C) range from –93.71 ± 1.77 (K-A) to –48.02 ± 1.85 kJ/mol per TO2 (Li-A) for hydrated alkali ion-exchanged zeolite A, and from –47.99 ± 1.20 (Ba-A) to –26.41 ± 1.71 kJ/mol per TO2 (Mg-A) for hydrated alkaline earth ion-exchanged zeolite A. As a result, the formation enthalpy from oxides generally becomes less exothermic as Z/r increases, but a distinct difference in slope is observed between the alkali and the alkaline earth series.

  14. Alkaline earth metal doped tin oxide as a novel oxygen storage material

    SciTech Connect

    Dong, Qiang; Yin, Shu; Yoshida, Mizuki; Wu, Xiaoyong; Liu, Bin; Miura, Akira; Takei, Takahiro; Kumada, Nobuhiro; Sato, Tsugio

    2015-09-15

    Alkaline earth metal doped tin oxide (SnO{sub 2}) hollow nanospheres with a diameter of 50 nm have been synthesized successfully via a facial solvothermal route in a very simple system composed of only ethanol, acetic acid, SnCl{sub 4}·5H{sub 2}O and A(NO{sub 3}){sub 2}·xH{sub 2}O (A = Mg, Ca, Sr, Ba). The synthesized undoped SnO{sub 2} and A-doped SnO{sub 2} hollow nanospheres were characterized by the oxygen storage capacity (OSC), X-ray diffraction, transmission electron microscopy and the Brunauer–Emmet–Teller (BET) technique. The OSC values of all samples were measured using thermogravimetric-differential thermal analysis. The incorporation of alkaline earth metal ion into tin oxide greatly enhanced the thermal stability and OSC. Especially, Ba-doped SnO{sub 2} hollow nanospheres calcined at 1000 °C for 20 h with a BET surface area of 61 m{sup 2} g{sup −1} exhibited the considerably high OSC of 457 μmol-O g{sup −1} and good thermal stability. Alkaline earth metal doped tin oxide has the potential to be a novel oxygen storage material.

  15. The Effect of Alkaline Earth Metal on the Cesium Loading of Ionsiv(R) IE-910 and IE-911

    SciTech Connect

    Fondeur, F.F.

    2001-01-16

    This study investigated the effect of variances in alkaline earth metal concentrations on cesium loading of IONSIV(R) IE-911. The study focused on Savannah River Site (SRS) ''average'' solution with varying amounts of calcium, barium and magnesium.

  16. Process optimization and kinetics for leaching of rare earth metals from the spent Ni-metal hydride batteries.

    PubMed

    Meshram, Pratima; Pandey, B D; Mankhand, T R

    2016-05-01

    Nickel-metal hydride batteries (Ni-MH) contain not only the base metals, but valuable rare earth metals (REMs) viz. La, Sm, Nd, Pr and Ce as well. In view of the importance of resource recycling and assured supply of the contained metals in such wastes, the present study has focussed on the leaching of the rare earth metals from the spent Ni-MH batteries. The conditions for the leaching of REMs from the spent batteries were optimized as: 2M H2SO4, 348K temperature and 120min of time at a pulp density (PD) of 100g/L. Under this condition, the leaching of 98.1% Nd, 98.4% Sm, 95.5% Pr and 89.4% Ce was achieved. Besides the rare earth metals, more than 90% of base metals (Ni, Co, Mn and Zn) were also leached out in this condition. Kinetic data for the dissolution of all the rare earth metals showed the best fit to the chemical control shrinking core model. The leaching of metals followed the mechanism involving the chemical reaction proceeding on the surface of particles by the lixiviant, which was corroborated by the XRD phase analysis and SEM-EDS studies. The activation energy of 7.6, 6.3, 11.3 and 13.5kJ/mol was acquired for the leaching of neodymium, samarium, praseodymium and cerium, respectively in the temperature range 305-348K. From the leach liquor, the mixed rare earth metals were precipitated at pH∼1.8 and the precipitated REMs was analyzed by XRD and SEM studies to determine the phases and the morphological features.

  17. Nano porous alkaline earth metal silicates as free fatty acid adsorbents from Crude Palm Oil (CPO)

    NASA Astrophysics Data System (ADS)

    Masmur, Indra; Sembiring, Seri Bima; Bangun, Nimpan; Kaban, Jamaran; Putri, Nabila Karina

    2017-01-01

    Free fatty acids(FFA) from Crude Palm Oil (CPO) have been adsorbed by alkaline earth metal silicate (M-silicate : M = Mg, Ca, Sr and Ba) adsorbents in ethanol using batch method. The adsorbents were prepared from the chloride salts of alkaline metals and Na2SiO3. The resulting white solid of the alkaline earth metal silicates were then heated at 800°C for 3 hours to enlarge their porosities. All adsorbents were characterized by SEM-EDX, XRD and BET. The EDX spectrum of SEM-EDX showed the appearance of all elements in the adsorbents, and the XRD spectrum of all adsorbents showed that they have crystobalite structure. The porosity of the adsorbents calculated by BET method showed that the porosities of the adsorbents range from 2.0884 - 2.0969 nm. All the adsorbents were used to adsorb the FFA from CPO containing 4.79%, 7.3%, 10.37% and 13.34% of FFA. The ratio of adsorbent to CPO to be used in adsorption of FFA from CPO were made 1:1, 1:2 and 1:3, with adsorption time of 1 hour. We found that the maximum adsorption of FFA from CPO was given by Ca-Silicate adsorbent which was between 69.86 - 94.78%, while the lowest adsorption was shown by Mg-silicate adsorbent which was 49.32 -74.53%.

  18. Intermolecular hydroamination of vinylarenes by iminoanilide alkaline-earth catalysts: a computational scrutiny of mechanistic pathways.

    PubMed

    Tobisch, Sven

    2014-07-14

    A thorough computational exploration of the mechanistic intricacies of the intermolecular hydroamination (HA) of vinylarenes by a recently reported class of kinetically stabilised iminoanilide [{N^N}Ae{N(SiMe3)2}⋅(THF)n] alkaline-earth amido compounds (Ae = Ca, Sr, Ba) is presented. Two distinct mechanistic pathways for catalytic HA mediated by alkaline-earth and rare-earth compounds have emerged over the years that account equally well for the specific features of the process. On one hand, a concerted proton-assisted pathway to deliver the amine product in a single step can be invoked and, on the other, a stepwise σ-insertive pathway that comprises a rapid, reversible migratory olefin insertion step linked to a less facile, irreversible Ae-C alkyl bond aminolysis. The results of the study presented herein, which employed a heavily benchmarked and reliable DFT methodology, supports a stepwise σ-insertive pathway that involves fast and reversible migratory C=C bond insertion into the polar Ae-N pyrrolido σ bond. This proceeds with strict 2,1 regioselectivity via a highly polarised four-centre transition state (TS) structure, linked to irreversible intramolecular Ae-C bond aminolysis of the alkaline-earth alkyl intermediate as the energetically favourable mechanism. Turnover-limiting aminolysis is consistent with the significant KIE measured; the DFT-derived effective barrier matches the Eyring parameter empirically determined for the best-performing {N^N}Ba(NR2) catalyst gratifyingly well. It also predicts the observed trend in reactivity (Ca

  19. Theoretical investigation of the structures, stabilities, and NLO responses of calcium-doped pyridazine: alkaline-earth-based alkaline salt electrides.

    PubMed

    Wang, Yin-Feng; Huang, Jiangen; Jia, Li; Zhou, Guangpei

    2014-02-01

    Currently, whether alkaline-earth-doped compounds with electride characteristics are novel candidates for high-performance nonlinear optical (NLO) materials is unknown. In this paper, using quantum chemical computations, we show that: when doping calcium atoms into a family of alkaline-substituted pyridazines, alkaline-earth-based alkaline salt electrides M-H₃C₄N₂⋯Ca (M=H, Li, and K) with distended excess electron clouds are formed. Interestingly, from the triplet to the singlet state, the chemical valence of calcium atom changes from +1 to 0, and the dipole moment direction (μ₀) of the molecule reverses for each M-H₃C₄N₂⋯Ca. Changing pyridazine from without (H₄C₄N₂⋯Ca) to with one alkaline substituent (M-H₃C₄N₂⋯Ca, M=Li and K), the ground state changes from the triplet to the singlet state. The alkaline earth metal doping effect (electride effect) and alkaline salt effect on the static first hyperpolarizabilities (β₀) demonstrates that (1) the β₀ value is increased approximately 1371-fold from 2 (pyridazine, H₄C₄N₂) to 2745au (Ca-doped pyridazine, H₄C₄N₂⋯Ca), (2) the β₀ value is increased approximately 1146-fold from 2 in pyridazine (H₄C₄N₂) to 2294au in an Li-substituted pyridazine (Li-H₃C₄N₂), and (3) the β₀ value is increased 324-(M=Li) and 106-(M=K) fold from 826 (MLi) and 2294au (MK) to 268,679 (M=Li) and 245,878au (M=K), respectively, from the alkalized pyridazine (M-H₃C₄N₂) to the Ca-doped pyridazine (M-H₃C₄N₂⋯Ca). These results may provide a new means for designing high-performance NLO materials.

  20. Nickel/metal hydride batteries using rate-earth hydrogen storage alloy

    NASA Astrophysics Data System (ADS)

    Chen, J.; Zhang, Y. S.

    1994-07-01

    Fine particles of a hydrogen storage alloy (LaNi3.8Co0.5Mn0.4Al0.3) were microencapsulated with a thin film of nickel of about 0.6 micron thickness. The microencapsulated alloy powders were used as an anode material in a sealed nickel/metal hydride battery. The battery characteristics were compared with those of a battery with a bare (uncoated) alloy anode. The battery using the bare alloy was less stable compared to the coated alloy due to the role of the coated nickel as an oxygen barrier for protecting the alloy surface from oxidation. In addition, charge- discharge characteristics were improved greatly by the nickel coating, especially at high rates and at low temperatures due to the role of nickel as a microcurrent collector. So the microencapsulation of the alloy powders improves the performances of the alloy electrode.

  1. LaNi{sub 5{minus}x}M{sub x} metal hydride alloys for alkaline rechargeable cells

    SciTech Connect

    Witham, C.K.; Hightower, A.; Bowman, R.C. Jr.; Fultz, B.; Ratnakumar, B.V.

    1997-12-01

    This work centers on making alloy modifications to LaNi{sub 5} by replacing Ni with various metal elements. The primary goal of the alloy modifications is to stabilize the alloy during electrochemical cycling in an alkaline medium. The reasons that some elements promote cyclic stability are explored, and the relative magnitude of their effect is Ge > Sn > Si > Ga > Al > In > Ni. Other properties are determined for each alloy, such as maximum capacity, charge transfer kinetics, hydrogen diffusion, charge overpotentials, and charge efficiency. Alloy microstructural information is measured by X-ray diffraction, and gas-phase.

  2. Quantum phase transition of alkaline-earth fermionic atoms confined in an optical superlattice

    NASA Astrophysics Data System (ADS)

    Silva-Valencia, J.; Franco, R.; Figueira, M. S.

    2013-03-01

    Using the density matrix renormalization group method, we evaluate the spin and charge gaps of alkaline-earth fermionic atoms in a periodic one-dimensional optical superlattice. The number of delocalized atoms is equal to the lattice size and we consider an antiferromagnetic coupling between delocalized and localized atoms. We found a quantum phase transition from a Kondo insulator spin liquid state without confining potential to a charge-gapped antiferromagnetic state with nonzero potential. For each on-site coupling, there is a critical potential point for which the spin gap vanishes and its value increases linearly with the local interaction.

  3. Single-stage sub-Doppler cooling of alkaline earth atoms.

    PubMed

    Xu, Xinye; Loftus, Thomas H; Dunn, Josh W; Greene, Chris H; Hall, John L; Gallagher, Alan; Ye, Jun

    2003-05-16

    We report the first experimental study of sub-Doppler cooling in alkaline earth atoms (87Sr) enabled by the presence of nuclear spin-originated magnetic degeneracy in the atomic ground state. Sub-Doppler cooling in a sigma(+)-sigma(-) configuration is achieved despite the presence of multiple, closely spaced excited states. This surprising result is confirmed by an expanded multilevel theory of the radiative cooling force. Detailed investigations of system performance have shed new insights into (sigma(+)-sigma(-)) cooling dynamics and will likely play an important role in the future development of neutral atom-based optical frequency standards.

  4. Wide-band-gap, alkaline-earth-oxide semiconductor and devices utilizing same

    DOEpatents

    Abraham, Marvin M.; Chen, Yok; Kernohan, Robert H.

    1981-01-01

    This invention relates to novel and comparatively inexpensive semiconductor devices utilizing semiconducting alkaline-earth-oxide crystals doped with alkali metal. The semiconducting crystals are produced by a simple and relatively inexpensive process. As a specific example, a high-purity lithium-doped MgO crystal is grown by conventional techniques. The crystal then is heated in an oxygen-containing atmosphere to form many [Li].degree. defects therein, and the resulting defect-rich hot crystal is promptly quenched to render the defects stable at room temperature and temperatures well above the same. Quenching can be effected conveniently by contacting the hot crystal with room-temperature air.

  5. Liquefaction process for solid carbonaceous materials containing alkaline earth metal humates

    DOEpatents

    Epperly, William R.; Deane, Barry C.; Brunson, Roy J.

    1982-01-01

    An improved liquefaction process wherein wall scale and particulate agglomeration during the liquefaction of solid carbonaceous materials containing alkaline earth metal humates is reduced and/or eliminated by subjecting the solid carbonaceous materials to controlled cyclic cavitation during liquefaction. It is important that the solid carbonaceous material be slurried in a suitable solvent or diluent during liquefaction. The cyclic cavitation may be imparted via pressure cycling, cyclic agitation and the like. When pressure cycling or the like is employed an amplitude equivalent to at least 25 psia is required to effectively remove scale from the liquefaction vessel walls.

  6. Studies on the interactions between purified bovine caseins and alkaline-earth-metalions

    PubMed Central

    Dickson, I. R.; Perkins, D. J.

    1971-01-01

    1. Alkaline-earth-metal cations at low concentrations form soluble complexes with bovine caseins. The relative order of binding capacities is: Mg2+>Ca2+>Ba2+>Sr2+. 2. The cations interact with both free ionized carboxyl groups of aspartic acid and glutamic acid and with monoester phosphate groups covalently bound to serine and threonine; at low concentrations of the cations interactions are predominantly with the phosphate groups. 3. The order of binding capacities for purified components of the casein complex is: αs1-casein>β-casein>κ-casein. PMID:5166590

  7. Novel polymerization catalysts and hydride clusters from rare-earth metal dialkyls.

    PubMed

    Nishiura, Masayoshi; Hou, Zhaomin

    2010-04-01

    This Review gives an overview on recent progress in the synthesis and chemistry of rare-earth metal dialkyl complexes bearing monoanionic ancillary ligands, with an emphasis on novel polymerization catalysts. These structurally well-defined and highly reactive compounds are prepared either by alkane elimination reactions between trialkyl rare-earth complexes and acidic neutral ligands, or by the metathetical reactions of rare-earth trihalides with the alkali metal salts of the corresponding ligands. On treatment with an appropriate borate compound, the dialkyl complexes are converted into the corresponding cationic monoalkyl species, which serve as excellent catalysts for the polymerization and copolymerization of a variety of olefins to yield a series of new polymer materials that exhibit novel properties. Alternatively, hydrogenation of the dialkyl rare-earth complexes with H(2) affords a new class of rare-earth polyhydride complexes with unique features in terms of both their structure and reactivity.

  8. Rare-earth metal hydrides supported by silicon-bridged boratabenzene fluorenyl ligands: synthesis, structure and reactivity.

    PubMed

    Wang, Chunhong; Xiang, Li; Leng, Xuebing; Chen, Yaofeng

    2017-01-24

    The reactions of rare-earth metal benzyl complexes supported by silicon-bridged boratabenzene fluorenyl ligands with PhSiH3 in toluene gave the corresponding dinuclear hydrides [{μ-[Me2Si(C13H8)(C5H4BNEt2)]}Ln(μ-H)(THF)]2 (3-Ln; Ln = La, Nd, Gd), wherein the rare-earth metal ions are linked by both silicon-bridged boratabenzene fluorenyl ligands and hydrido ligands. The reactivity of these hydrides toward unsaturated substrates was studied. Among these, alkynides [{μ-[Me2Si(C13H8)(C5H4BNEt2)]}Ln(μ-CCPh)]2 (4-Ln; Ln = La, Nd) were obtained via the σ-bond metathesis reaction, when 3-Ln (Ln = La, Nd) was treated with phenylacetylene. While reacting with 3-hexyne, the mono-addition product [{μ-[Me2Si(C13H8)(C5H4BNEt2)]}Ln]2(μ-H)[μ-C(Et)[double bond, length as m-dash]C(H)Et] (5-Ln; Ln = La, Nd) was formed. Further investigations on the reactivity of 3-La displayed that benzonitrile and tert-butyl isonitrile readily inserted into the La-H bonds, affording an azomethine complex [{μ-[Me2Si(C13H8)(C5H4BNEt2)]}La{μ-N[double bond, length as m-dash]C(H)Ph}]2 (6-La) and an N-tert-butylformimidoyl complex [{μ-[Me2Si(C13H8)(C5H4BNEt2)]}La{μ,η(2)-C(H)[double bond, length as m-dash]N(t)Bu}]2 (7-La), respectively. The reaction with N,N'-diisopropylcarbodiimide at room temperature or at 75 °C gave a dimeric complex [{μ-[Me2Si(C13H8)(C5H4BNEt2)]}La]2(μ-H)[μ-N((i)Pr)CHN((i)Pr)] (8-La) or a monomeric complex [Me2Si(C13H8)(C5H4BNEt2)]La[N((i)Pr)CHN((i)Pr)] (9-La), respectively.

  9. Measurements of the mobility of alkaline earth ions in liquid xenon

    NASA Astrophysics Data System (ADS)

    Jeng, S.-C.; Fairbank, W. M., Jr.; Miyajima, M.

    2009-02-01

    The mobility of alkaline earth ions, Mg+, Ca+, Sr+ and Ba+, in liquid xenon is measured for the first time. The mobility of Tl+ is also determined for comparison with a measurement by other researchers. The Atkins cluster model for positive ions in non-polar liquids, based on the electrostriction effect, gives general agreement with the magnitude of the mobility values. This is some evidence that the positive ions form a snowball rather than a bubble structure in liquid xenon. However, the temperature dependence of the mobility does not match well with the Atkins theory, so there are still open theoretical questions on the nature of the environment of alkaline earth ions in liquid xenon. The lower mobility of Mg+ and Ba+ may be explained by a better size match to interstitial and substitutional sites, respectively, in solid Xe. These measurements are motivated by the development of a new technique to search for neutrino masses through 0νββ decay of 136Xe. A key component of one version of the proposed experiment is tagging of 136Ba+ daughter ions in liquid 136Xe by laser-induced fluorescence.

  10. Atomic hydrogen in. gamma. -irradiated hydroxides of alkaline-earth elements

    SciTech Connect

    Spitsyn, V.I.; Yurik, T.K.; Barsova, L.I.

    1982-04-01

    Atomic hydrogen is an important intermediate product formed in the radiolysis of compounds containing X-H bonds. H atoms have been detected in irradiated matrices of H/sub 2/ and inert gases at 4/sup 0/K, in irradiated ice and frozen solutions of acids in irradiated salts and in other systems. Here results are presented from a study of the ESR spectra of H atoms generated in polycrystalline hydroxides of alkaline-earth elements that have been ..gamma..-irradiated at 77/sup 0/K, after preliminary treatment at various temperatures. For the first time stabilization of atomic hydrogen in ..gamma..-irradiated polycrystalline alkaline-earth element hydroxides has been detected. Depending on the degree of dehydroxylation, several types of hydrogen atoms may be stabilized in the hydroxides, these hydrogen atoms having different radiospectroscopic parameters. In the magnesium-calcium-strontium-barium hydroxide series, a regular decrease has been found in the hfi constants for H atoms with the cations in the immediate surroundings. A direct proportionality has been found between the parameters ..delta..A/A/sub 0/ and the polarizability of the cation.

  11. Temperature-induced collapse of alkaline Earth cation-polyacrylate anion complexes.

    PubMed

    Lages, Sebastian; Schweins, Ralf; Huber, Klaus

    2007-09-06

    Polyacrylate anions are used to inhibit CaCO3 precipitation and may be a promising additive to control formation of inorganic nanoparticles. The origin of this applicability lies in specific interactions between the alkaline earth cations and the carboxylate functions along the polyacrylate chains. In the absence of CO32- anions, these interactions eventually cause precipitation of polyelectrolytes. Extended investigation of dilute sodium polyacrylate solutions approaching this precipitation threshold revealed a dramatic shrinking of the PA coil dimensions once the threshold is reached (Eur. Phys. J. E 2001, 5, 117). Recent isothermal calorimetric titration experiments by Antonietti et al. (Macromolecules 2004, 37, 3444) indicated that the driving force of this precipitation is entropic in nature. In the present work, we investigated the impact of temperature on the structural changes of dissolved polyacrylate chains decorated with alkaline earth cations. To this end, large polyacrylate chains were brought close to the precipitation threshold by the addition of distinct amounts of Ca2+ or Sr2+ cations. The resulting structural intermediates were then subjected to temperature variations in the range of 15 degrees C

  12. Tungstate-ferrates of some alkali and alkaline-earth metals

    SciTech Connect

    Gruba, A.I.; Danileiko, L.A.; Moroz, Ya.A.; Zyats, M.N.

    1988-02-01

    Tungstate-ferrates of some alkali and alkaline-earth metals with the ratio Fe:W = 2:11, the iron ions in which are found in two types of coordination, tetrahedral and octahedral, were synthesized. The similarity of the IR spectra of the compounds obtained and known compounds with the anion structure of the Keggin type with the composition M/sub X/(XZW/sub 11/O/sub 40/H/sub m/) x nH/sub 2/O indicates that their heteropolyanions are isostructural. The thermal stability of the compounds studied and the structure of the products of thermolysis depend on the charge and radius of the extrasphere cation. When the ratio of the radii of the extrasphere cation of the alkali or alkaline-earth metal to the radius of the ion of the central 3d element, appearing in the coordination sphere of the heteropolytungstates, exceeds 1.6, the most likely products of thermolysis of heteropolycompounds are the compounds of the pyrochlore family and tungsten bronzes.

  13. Matrix diffusion of some alkali- and alkaline earth-metals in granitic rock

    SciTech Connect

    Johansson, H.; Byegaard, J.; Skarnemark, G.; Skaalberg, M.

    1997-12-31

    Static through-diffusion experiments were performed to study the diffusion of alkali- and alkaline earth-metals in fine-grained granite and medium-grained Aespoe-diorite. Tritiated water was used as an inert reference tracer. Radionuclides of the alkali- and alkaline earth-metals (mono- and divalent elements which are not influenced by hydrolysis in the pH-range studied) were used as tracers, i.e., {sup 22}Na{sup +}, {sup 45}Ca{sup 2+} and {sup 85}Sr{sup 2+}. The effective diffusivity and the rock capacity factor were calculated by fitting the breakthrough curve to the one-dimensional solution of the diffusion equation. Sorption coefficients, K{sub d}, that were derived from the rock capacity factor (diffusion experiments) were compared with K{sub d} determined in batch experiments using crushed material of different size fractions. The results show that the tracers were retarded in the same order as was expected from the measured batch K{sub d}. Furthermore, the largest size fraction was the most representative when comparing batch K{sub d} with K{sub d} evaluated from the diffusion experiments. The observed effective diffusivities tended to decrease with increasing cell lengths, indicating that the transport porosity decreases with increasing sample lengths used in the diffusion experiments.

  14. Three-photon process for producing a degenerate gas of metastable alkaline-earth-metal atoms

    NASA Astrophysics Data System (ADS)

    Barker, D. S.; Pisenti, N. C.; Reschovsky, B. J.; Campbell, G. K.

    2016-05-01

    We present a method for creating a quantum degenerate gas of metastable alkaline-earth-metal atoms. This has yet to be achieved due to inelastic collisions that limit evaporative cooling in the metastable states. Quantum degenerate samples prepared in the 1S0 ground state can be rapidly transferred to either the 3P2 or 3P0 state via a coherent three-photon process. Numerical integration of the density-matrix evolution for the fine structure of bosonic alkaline-earth-metal atoms shows that transfer efficiencies of ≃90 % can be achieved with experimentally feasible laser parameters in both Sr and Yb. Importantly, the three-photon process can be set up such that it imparts no net momentum to the degenerate gas during the excitation, which will allow for studies of metastable samples outside the Lamb-Dicke regime. We discuss several experimental challenges to successfully realizing our scheme, including the minimization of differential ac Stark shifts between the four states connected by the three-photon transition.

  15. A 3-photon process for producing degenerate gases of metastable alkaline-earth atoms

    NASA Astrophysics Data System (ADS)

    Barker, Daniel S.; Pisenti, Neal C.; Reschovsky, Benjamin J.; Campbell, Gretchen K.

    2016-05-01

    We present a method for creating quantum degenerate gases of metastable alkaline-earth atoms. A degenerate gas in any of the 3 P metastable states has not previously been obtained due to large inelastic collision rates, which are unfavorable for evaporative cooling. Samples prepared in the 1S0 ground state can be rapidly transferred to either the 3P2 or 3P0 state via a coherent 3-photon process. Numerical integration of the density matrix evolution for the fine structure of bosonic alkaline-earth atoms shows that transfer efficiencies of ~= 90 % can be achieved with experimentally feasible laser parameters in both Sr and Yb. Importantly, the 3-photon process does not impart momentum to the degenerate gas during excitation, which allows studies of these metastable samples outside the Lamb-Dicke regime. We discuss several experimental challenges to the successful realization of our scheme, including the minimization of differential AC Stark shifts between the four states connected by the 3-photon transition.

  16. Theoretical study of the alkaline-earth metal superoxides BeO2 through SrO2

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Partridge, Harry; Sodupe, Mariona; Langhoff, Stephen R.

    1992-01-01

    Three competing bonding mechanisms have been identified for the alkaline-earth metal superoxides: these result in a change in the optimal structure and ground state as the alkaline-earth metal becomes heavier. For example, BeO2 has a linear 3Sigma(-)g ground-state structure, whereas both CaO2 and SrO2 have C(2v)1A1 structures. For MgO2, the theoretical calculations are less definitive, as the 3A2 C(2v) structure is computed to lie only about 3 kcal/mol above the 3Sigma(-)g linear structure. The bond dissociation energies for the alkaline-earth metal superoxides have been computed using extensive Gaussian basis sets and treating electron correlation at the modified coupled-pair functional or coupled-cluster singles and doubles level with a perturbational estimate of the triple excitations.

  17. Bond-length distributions for ions bonded to oxygen: alkali and alkaline-earth metals

    PubMed Central

    Gagné, Olivier Charles; Hawthorne, Frank Christopher

    2016-01-01

    Bond-length distributions have been examined for 55 configurations of alkali-metal ions and 29 configurations of alkaline-earth-metal ions bonded to oxygen, for 4859 coordination polyhedra and 38 594 bond distances (alkali metals), and for 3038 coordination polyhedra and 24 487 bond distances (alkaline-earth metals). Bond lengths generally show a positively skewed Gaussian distribution that originates from the variation in Born repulsion and Coulomb attraction as a function of interatomic distance. The skewness and kurtosis of these distributions generally decrease with increasing coordination number of the central cation, a result of decreasing Born repulsion with increasing coordination number. We confirm the following minimum coordination numbers: [3]Li+, [3]Na+, [4]K+, [4]Rb+, [6]Cs+, [3]Be2+, [4]Mg2+, [6]Ca2+, [6]Sr2+ and [6]Ba2+, but note that some reported examples are the result of extensive dynamic and/or positional short-range disorder and are not ordered arrangements. Some distributions of bond lengths are distinctly multi-modal. This is commonly due to the occurrence of large numbers of structure refinements of a particular structure type in which a particular cation is always present, leading to an over-representation of a specific range of bond lengths. Outliers in the distributions of mean bond lengths are often associated with anomalous values of atomic displacement of the constituent cations and/or anions. For a sample of [6]Na+, the ratio U eq(Na)/U eq(bonded anions) is partially correlated with 〈[6]Na+—O2−〉 (R 2 = 0.57), suggesting that the mean bond length is correlated with vibrational/displacement characteristics of the constituent ions for a fixed coordination number. Mean bond lengths also show a weak correlation with bond-length distortion from the mean value in general, although some coordination numbers show the widest variation in mean bond length for zero distortion, e.g. Li+ in [4]- and [6]-coordination, Na+ in [4]- and [6

  18. Structure elucidation of alkaline earth impregnated MCM-41 type mesoporous materials obtained by direct synthesis: An experimental and theoretical study

    NASA Astrophysics Data System (ADS)

    Paz, Gizeuda L.; Silva, Francisco das Chagas M.; Araújo, Maciel M.; Lima, Francisco das Chagas A.; Luz, Geraldo E.

    2014-06-01

    In this work, MCM-41 were synthesized hydrothermally and functionalized with calcium and strontium salts by direct method, using the Si/M = 50 molar ratio, in order to elucidate the way as the alkaline earth is incorporated on MCM-41 molecular sieve. The materials were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, nitrogen adsorption-desorption and theoretical calculations by DFT method. Experimental results and computer simulations showed that the alkaline earths were incorporated on MCM-41 through a complex structure, which negatively influences on basic sites formation.

  19. Impacts of artificial ocean alkalinization on the carbon cycle and climate in Earth system simulations

    NASA Astrophysics Data System (ADS)

    González, Miriam Ferrer; Ilyina, Tatiana

    2016-06-01

    Using the state-of-the-art emissions-driven Max Planck Institute Earth system model, we explore the impacts of artificial ocean alkalinization (AOA) with a scenario based on the Representative Concentration Pathway (RCP) framework. Addition of 114 Pmol of alkalinity to the surface ocean stabilizes atmospheric CO2 concentration to RCP4.5 levels under RCP8.5 emissions. This scenario removes 940 GtC from the atmosphere and mitigates 1.5 K of global warming within this century. The climate adjusts to the lower CO2 concentration preventing the loss of sea ice and high sea level rise. Seawater pH and the carbonate saturation state (Ω) rise substantially above levels of the current decade. Pronounced differences in regional sensitivities to AOA are projected, with the Arctic Ocean and tropical oceans emerging as hot spots for biogeochemical changes induced by AOA. Thus, the CO2 mitigation potential of AOA comes at a price of an unprecedented ocean biogeochemistry perturbation with unknown ecological consequences.

  20. Theoretical study of the alkaline-earth (LiBe)+ ion: structure, spectroscopy and dipole moments

    NASA Astrophysics Data System (ADS)

    Ghanmi, C.; Farjallah, M.; Berriche, H.

    2017-03-01

    We study theoretically the structure and spectroscopic properties of the alkali alkaline-earth (LiBe)+ ion. The potential energy curves and their spectroscopic parameters, permanent and transition dipole moments are determined with a quantum chemistry approach. The (LiBe)+ ion is modelled as two valence electron system moving in the field of Be2+ and Li+ cores, which are described by pseudopotentials. In addition, effective core-polarization potentials are included to correct the energy. The molecular calculations are performed using a standard quantum chemistry approach based on the pseudopotential model, Gaussian basis sets, effective core polarization potentials, and full configuration interaction (CI) calculations. The precision of our spectroscopic parameters are discussed by comparison with currently available theoretical results. A rather good agreement is observed for the ground and first excited states. The permanent dipole moments reveal many abrupt changes, which are localized at particular distances corresponding to the positions of the avoided crossings.

  1. Prolonged QT Syndrome and Seizure Secondary to Alkaline Earth Metal Deficiency: A Case Report.

    PubMed

    McKinney, A; Keegan, B C

    2011-01-01

    Introduction. Alkaline earth metal deficiency is recognized as a cause of both seizure and long QT syndrome. Their deficiency can have significant repercussions on the function of cells, tissues, and organs of the body. An understanding of the role of electrolytes allows an appreciation of the significance of depleted levels on cell function. Case Report. A 65-year-old lady was admitted with symptoms of chest discomfort, vomiting, increased stoma output, and dizziness. Two days following admission she suffered a tonic-clonic seizure. ECG review demonstrated a prolonged QTc interval, raising the possibility of an underlying Torsades de Pointes as the precipitant. This was attributed to electrolyte disturbance arising as a result of multiple aetiologies. Discussion. This paper highlights the multisystem effects of electrolyte disturbance, with emphasis upon its role in precipitating cardiac arrhythmia and neurological symptoms.

  2. Alkaline earth metal cation exchange: effect of mobile counterion and dissolved organic matter.

    PubMed

    Indarawis, Katrina; Boyer, Treavor H

    2012-04-17

    The goal of this research was to provide an improved understanding of the interactions between alkaline earth metals and DOM under conditions that are encountered during drinking water treatment with particular focus on cation exchange. Both magnetically enhanced and nonmagnetic cation exchange resins were converted to Na, Mg, Ca, Sr, and Ba mobile counterion forms as a novel approach to investigate the exchange behavior between the cations and the interactions between the cations and DOM. The results show that cation exchange is a robust process for removal of Ca(2+) and Mg(2+) considering competition with cations on the resin surface and presence of DOM. DOM was actively involved during the cation exchange process through complexation, adsorption, and coprecipitation reactions. In addition to advancing the understanding of ion exchange processes for water treatment, the results of this work are applicable to membrane pretreatment to minimize fouling, treatment of membrane concentrate, and precipitative softening.

  3. Hydration process of alkaline-earth metal atoms in water clusters

    NASA Astrophysics Data System (ADS)

    Okai, Nobuhiro; Ishikawa, Haruki; Fuke, Kiyokazu

    2005-10-01

    Ionization potentials (IPs) of water clusters containing alkaline-earth metal atoms are measured by a photoionization threshold method to examine the hydration process of the metal atoms in clusters. IPs of Mg(H 2O) n and Ca(H 2O) n are found to decrease with increasing n and become constant at 3.18 eV for n ⩾ 9 and n ⩾ 8, respectively. The observed constant IP agrees with an estimated photoelectric threshold (3.2 eV) of bulk ice. From the comparison with the results on the theoretical calculations as well as the IPs for alkali atom-water clusters, the anomalous size dependence of IPs is ascribed to the formation of an ion-pair state.

  4. Linear alkaline earth metal phosphinate coordination polymers: synthesis and structural characterization.

    PubMed

    Rood, Jeffrey A; Huttenstine, Ashley L; Schmidt, Zachery A; White, Michael R; Oliver, Allen G

    2014-06-01

    Reaction of alkaline earth metal salts with diphenylphosphinic acid in dimethylformamide solvent afforded four coordination polymers: [Mg3(O2PPh2)6(DMF)2]·2DMF (I), [Ca(O2PPh2)2(DMF)2] (II), [Sr(O2PPh2)2(DMF)2] (III) and [Ba(O2PPh2)2(DMF)2] (IV) (where DMF is N,N-dimethylformamide). Single-crystal X-ray diffraction revealed that all four compounds produce linear chain structures in the solid state, with the Ca, Sr and Ba forming isostructural crystals. The bulk materials were characterized by FT-IR and (1)H NMR spectroscopy and elemental analyses.

  5. Magnetic crystals and helical liquids in alkaline-earth fermionic gases

    PubMed Central

    Barbarino, Simone; Taddia, Luca; Rossini, Davide; Mazza, Leonardo; Fazio, Rosario

    2015-01-01

    The joint action of a magnetic field and of interactions is crucial for the appearance of exotic quantum phenomena, such as the quantum Hall effect. Owing to their rich nuclear structure, equivalent to an additional synthetic dimension, one-dimensional alkaline-earth(-like) fermionic gases with synthetic gauge potential and atomic contact repulsion may display similar related properties. Here we show the existence and the features of a hierarchy of fractional insulating and conducting states by means of analytical and numerical methods. We demonstrate that the gapped states are characterized by density and magnetic order emerging solely for gases with effective nuclear spin larger than 1/2, whereas the gapless phases can support helical modes. We finally argue that these states are related to an unconventional fractional quantum Hall effect in the thin-torus limit and that their properties can be studied in state-of-the-art laboratories. PMID:26350624

  6. Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite

    DOEpatents

    Tierney, J.W.; Wender, I.; Palekar, V.M.

    1995-01-24

    The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100--160 C and the pressure range of 40--65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H[sub 2]/CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

  7. Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite

    DOEpatents

    Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

    1995-01-01

    The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

  8. Quantum Degenerate Mixtures of Alkali and Alkaline-Earth-Like Atoms

    SciTech Connect

    Hara, Hideaki; Takasu, Yosuke; Yamaoka, Yoshifumi; Doyle, John M.; Takahashi, Yoshiro

    2011-05-20

    We realize simultaneous quantum degeneracy in mixtures consisting of the alkali and alkaline-earth-like atoms Li and Yb. This is accomplished within an optical trap by sympathetic cooling of the fermionic isotope {sup 6}Li with evaporatively cooled bosonic {sup 174}Yb and, separately, fermionic {sup 173}Yb. Using cross-thermalization studies, we also measure the elastic s-wave scattering lengths of both Li-Yb combinations, |a{sub {sup 6}Li-{sup 174}Yb}|=1.0{+-}0.2 nm and |a{sub {sup 6}Li-{sup 173}Yb}|=0.9{+-}0.2 nm. The equality of these lengths is found to be consistent with mass-scaling analysis. The quantum degenerate mixtures of Li and Yb, as realized here, can be the basis for creation of ultracold molecules with electron spin degrees of freedom, studies of novel Efimov trimers, and impurity probes of superfluid systems.

  9. First hyperpolarizability of cyclooctatetraene modulated by alkali and alkaline earth metals.

    PubMed

    Roy, Ria Sinha; Mondal, Avijit; Nandi, Prasanta K

    2017-03-01

    In the present investigation, the first hyperpolarizability of alkali and alkaline earth metal derivatives of cyclooctatetraene (COT) has been calculated using BHHLYP and CAM-B3LYP functional for 6-311++G(d,p), 6-311++G(3df,3pd), and aug-pc 2 basis sets. Introduction of Na/K atoms at the axial position of COT and Li, Na, K/Be, Mg, Ca metal atoms and cyanide groups at the equatorial sites leads to lager enhancement of first hyperpolarizability. The ring charge density can account for the variation of first hyperpolarizability. The two state model has been invoked to explain the variation of first hyperpolarizability.

  10. Relationship between microstructure and efficiency of lithium silicate scintillating glasses: The effect of alkaline earths

    SciTech Connect

    Bliss, M.; Craig, R.A.; Sunberg, D.S.; Weber, M.J.

    1996-12-31

    Lithium silicate glasses containing Ce{sup 3+} are known to be scintillators. Glasses in this family in which the Li is enriched ({sup 6}Li) are used as neutron detectors. The addition of Mg to this glass is known to increase the scintillation efficiency. We have found that substituting other alkaline earths results in a monotonic decrease of the scintillation efficiency with increasing atomic number. The total variation in scintillation efficiency from Mg to Ba is nearly a factor of 3. Prior experiments with this glass family show small differences in Raman and fluorescence spectra; evidence from thermoluminescence experiments indicates that the scintillation efficiency is most strongly correlated with structural effects in the neighborhood of the Ce{sup 3+} activator ion. The results of low-temperature studies of fluorescence and thermoluminescence of these glasses will be reported.

  11. Effect of Composition and Impurities on the Phosphorescence of Green-Emitting Alkaline Earth Aluminate Phosphor

    PubMed Central

    Kim, Doory; Kim, Han-Eol; Kim, Chang-Hong

    2016-01-01

    Recent improvements to SrAl2O4:Eu2+, Dy3+ phosphors have enabled the use of luminescent hosts with a stable crystal structure and high physical and chemical stability, thus overcoming the bottleneck in the applicability of ZnS:Cu phosphors. However, enhancement of afterglow lifetime and brightness in SrAl2O4:Eu2+, Dy3+ phosphors remains a challenging task. Here, we have improved the afterglow characteristics in terms of persistence time and brightness by a systematic investigation of the composition of Eu-doped alkaline earth aluminate SrAl2O4:Eu2+, Dy3+ crystals. We found that a Dy3+/Eu2+ ratio of ~2.4 and ~0.935 mol Eu2+ (per mol of SrAl2O4) gave the brightest and longest emissions (11% and 9% increase for each). Doping with Si4+ also resulted in a slight increase in brightness up to ~15%. Doping with alkali metal or alkaline earth metal significantly enhanced the phosphorescence intensity. In particular, doping with 0.005 mol Li+ (per mol of SrAl2O4) alone boosted the phosphorescence intensity to 239% of the initial value, as compared to that observed for the non-doped crystal, while doping with 0.01 mol Mg2+ and 0.005 mol Li+ (per 1 mol SrAl2O4) boosted the phosphorescence intensity up to 313% of the initial value. The results of this investigation are expected to act as a guideline for the synthesis of bright and long persistent phosphors, and facilitate the development of persistent phosphors with afterglow characteristics superior to those of conventional phosphors. PMID:26731086

  12. Alkaline earth-based coordination polymers derived from a cyclotriphosphazene-functionalized hexacarboxylate

    NASA Astrophysics Data System (ADS)

    Ling, Yajing; Bai, Dongjie; Feng, Yunlong; He, Yabing

    2016-10-01

    Combination of hexakis(4-carboxylatephenoxy)cyclotriphosphazene with alkaline earth ions of increasing ionic radii (Mg2+, Ca2+ and Ba2+) under different solvothermal conditions yielded three new coordination polymers, and their crystal structures were determined by single-crystal X-ray diffraction analysis. The magnesium compound displays a three dimensional (3D) network structure constructed from the deprotonated ligand and the secondary building block Mg(COO)4, which can be rationalized as a (4,6)-connected topological net with the Schläfli symbol of (44·62)3(49·66)2. The calcium compound consists of 1D infinite "Ca-O" inorganic chains connected by the deprotonated ligands to from a 3D framework. The barium compound exhibits a 3D framework in which 1D "Ba-O" inorganic chains are connected together by the deprotonated organic linkers. Due to the semi-rigid nature, the ligand adopts distinctly different conformations in the three compounds. The metal ions' influence exerted on the final structure of the resulting coordination polymers is also discussed. When the radii of alkaline earth ions increases descending down the group from Mg(II) to Ba(II), the coordination number becomes larger and more versatile: from 6 in the magnesium compound, to 6,7 and 10 in the calcium compound, and to 8 and 9 in the barium compound, thus substantially influencing the resulting final framework structures. Also, the photophysical properties were investigated systematically, revealing that the three compounds are photoluminscent in the solid state at room temperature. This work demonstrates that although the multiplicity of conformation in the hexacarboxylate ligand based on the inorganic scaffold cyclotriphosphazene makes it difficult to predict how this ligand will form extended network, but provides unique opportunities for the formation of diverse inorganic-organic hybrids exhibiting rich structural topologies.

  13. 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)

  14. Optical and electronic properties of conductive ternary nitrides with rare- or alkaline-earth elements

    NASA Astrophysics Data System (ADS)

    Kassavetis, S.; Hodroj, A.; Metaxa, C.; Logothetidis, S.; Pierson, J. F.; Patsalas, P.

    2016-12-01

    Conductive nitrides, such as TiN, are key engineering materials for electronics, photonics, and plasmonics; one of the essential issues for such applications is the ability of tuning the conduction electron density, the resistivity, and the electron scattering. While enhancing the conduction electron density and blueshifting the intraband absorption towards the UV were easily achieved previously, reducing the conduction electron density and redshifting the intraband absorption into the infrared are still an open issue. The latter is achieved in this work by alloying TiN by rare earth (RE = Sc, Y, La) or alkaline earth (AE = Mg, Ca) atoms in Ti substitutional positions. The produced TixRE1-xN and TixAE1-xN thin film samples were grown by a hybrid arc evaporation/sputtering process, and most of them are stable in the B1 cubic structure. Their optical properties were studied in an extensive spectral range by spectroscopic ellipsometry. The ellipsometric spectra were analyzed and quantified by the Drude-Lorentz model, which provided the conduction electron density, the electron mean free path, and the resistivity. The observed interband transitions are firmly assigned, and the optical and electrical properties of TixRE1-xN and TixAE1-xN are quantitatively correlated with their composition and crystal structure.

  15. Alkaline earth metal fluxes for the growth of single crystal oxides

    NASA Astrophysics Data System (ADS)

    Ramirez, Daniel

    Oxide ceramics are materials with a wide range of properties. Insulators are most common, however semiconductors, strongly correlated electron materials, and even superconductors are all relevant oxide materials. Here we seek to synthesize novel oxide single crystal phases and study their properties using an alkaline earth metal flux technique. The specific flux techniques are new, and we will seek to understand the capabilities of these fluxes as a novel synthesis tool. The use of a barium metal flux to grow single crystal oxides is rather counterintuitive, but is exemplified further with the growth of europium monoxide (Fm3¯m #225, Z = 4). Eu1-xBaxO single crystals (x = 0.01 - 0.25) are grown and studied for their ferromagnetic properties. A new oxide phase Ba2Eu2P2O (P4/mbm #127, Z = 2) has also been synthesized from the same method, and may potentially be studied as a ferromagnetic semiconductor based on preliminary observations. Other examples of single crystal oxide phases grown from barium metal flux includes Ba2TeO (P4/nmm #129, Z = 2), BaLn2O4 (Ln = La - Lu) (Pnma #62, Z = 4), and Ba3Yb2O 5Te (P4/mmm #123 Z = 1). The new crystal phases Ba3Ln2O5Cl 2 (Ln = Sm - Lu, Y) are synthesized using a reactive barium metal flux. Single crystal x-ray diffraction is used to determine their structures with space group (I4/mmm #139, Z = 2) related to the Ruddlesden-Popper structure type. The unit cell dimensions range from a = 4.46(6) A and c = 24.87(6) A for Ba3Gd2O5Cl2 to a = 4.35(6) A and c = 24.57(6) A for Ba3Lu2O 5Cl2 with the dimensions following the expected lanthanide contraction trends. The magnetic properties of these materials are studied and related to their structures. The use of alkaline earth fluxes such as magnesium or calcium based fluxes are also briefly considered for their capabilities to produce novel mixed anion phases. A calcium flux is shown to produce the novel semimetals Ca 4TeOH4 and Ca3Ca1-xEuxTeOH 4 (I4/mmm #139, Z = 2), and highly reducing

  16. Bond ionicity of alkaline-earth oxides studied by low-energy D+ scattering

    NASA Astrophysics Data System (ADS)

    Souda, R.; Yamamoto, K.; Hayami, W.; Aizawa, T.; Ishizawa, Y.

    1994-08-01

    Low-energy D+ scattering is employed to explore the nature of the bonding of polycrystalline alkaline-earth oxides MgO, CaO, SrO, and BaO, with particular emphasis on the investigation of the ionicity of the topmost-layer atoms. Increasing ionicity as one goes to the heavier cations is concluded from the probability of the resonance neutraliztion of the D+ ions, which is consistent with the conventional chemical arguments based on electronegativity scales but is in apparent contradiction to the results of recent ab initio cluster-model calculations. It is also concluded that the metallic Ba layer is formed rather patchily on the BaO surface after the heat treatment up to 1000 °C. This is probably because free Ba atoms, being supplied by the reaction of BaO with the Ta substrate, are precipitated at the BaO surface. Another example is concerned with the interactions of the Ba adatoms with Si(001) and Pt(111) surfaces; Ba is found to have marked covalency with the substrate atoms.

  17. CP(N - 1) quantum field theories with alkaline-earth atoms in optical lattices

    NASA Astrophysics Data System (ADS)

    Laflamme, C.; Evans, W.; Dalmonte, M.; Gerber, U.; Mejía-Díaz, H.; Bietenholz, W.; Wiese, U.-J.; Zoller, P.

    2016-07-01

    We propose a cold atom implementation to attain the continuum limit of (1 + 1) -d CP(N - 1) quantum field theories. These theories share important features with (3 + 1) -d QCD, such as asymptotic freedom and θ-vacua. Moreover, their continuum limit can be accessed via the mechanism of dimensional reduction. In our scheme, the CP(N - 1) degrees of freedom emerge at low energies from a ladder system of SU(N) quantum spins, where the N spin states are embodied by the nuclear Zeeman states of alkaline-earth atoms, trapped in an optical lattice. Based on Monte Carlo results, we establish that the continuum limit can be demonstrated by an atomic quantum simulation by employing the feature of asymptotic freedom. We discuss a protocol for the adiabatic preparation of the ground state of the system, the real-time evolution of a false θ-vacuum state after a quench, and we propose experiments to unravel the phase diagram at non-zero density.

  18. Crystal and defect chemistry influences on band gap trends in alkaline earth perovskites

    SciTech Connect

    Lee, Soonil; Woodford, William H.; Randall, Clive A.

    2008-05-19

    A number of perovskites with A-site alkaline earth chemistries being Ca, Sr, and Ba, and tetravalent cations including Ce, Zr, and Ti are measured for optical band gap and found to vary systematically with tolerance factor and lattice volume within limits defined by the chemistry of the octahedral site. This paper also focuses on the BaTiO{sub 3} system, considering equilibrated nonstoichiometries, and determines the changes in band gap with respect to Ba/Ti ratios. It was found that the optical band gap changes in the solid solution regime and is invariant in the second phase regions, as would be expected. In the cases of Ba/Ti<1.0, the variation in band gap scales with lattice volume, but in the Ba/Ti>1.0 stoichiometries, there is a distinct Urbach tail and the trend with lattice volume no longer holds. It is inferred that the V{sub Ti}{sup q}prime-2V{sub O} partial Schottky complex controls the band gap trend with Ba-rich nonstoichiometries.

  19. Collective non-equilibrium spin exchange in cold alkaline-earth atomic clocks

    NASA Astrophysics Data System (ADS)

    Acevedo, Oscar Leonardo; Rey, Ana Maria

    2016-05-01

    Alkaline-earth atomic (AEA) clocks have recently been shown to be reliable simulators of two-orbital SU(N) quantum magnetism. In this work, we study the non-equilibrium spin exchange dynamics during the clock interrogation of AEAs confined in a deep one-dimensional optical lattice and prepared in two nuclear levels. The two clock states act as an orbital degree of freedom. Every site in the lattice can be thought as populated by a frozen set of vibrational modes collectively interacting via predominantly p-wave collisions. Due to the exchange coupling, orbital state transfer between atoms with different nuclear states is expected to happen. At the mean field level, we observe that in addition to the expected suppression of population transfer in the presence of a large magnetic field, that makes the single particle levels off-resonance, there is also an interaction induced suppression for initial orbital population imbalance. This suppression resembles the macroscopic self-trapping mechanism seen in bosonic systems. However, by performing exact numerical solutions and also by using the so-called Truncated Wigner Approximation, we show that quantum correlations can significantly modify the mean field suppression. Our predictions should be testable in optical clock experiments. Project supported by NSF-PHY-1521080, JILA-NSF-PFC-1125844, ARO, AFOSR, and MURI-AFOSR.

  20. Process for depositing epitaxial alkaline earth oxide onto a substrate and structures prepared with the process

    DOEpatents

    McKee, Rodney A.; Walker, Frederick J.

    1996-01-01

    A process and structure involving a silicon substrate utilize molecular beam epitaxy (MBE) and/or electron beam evaporation methods and an ultra-high vacuum facility to grow a layup of epitaxial alkaline earth oxide films upon the substrate surface. By selecting metal constituents for the oxides and in the appropriate proportions so that the lattice parameter of each oxide grown closely approximates that of the substrate or base layer upon which oxide is grown, lattice strain at the film/film or film/substrate interface of adjacent films is appreciably reduced or relieved. Moreover, by selecting constituents for the oxides so that the lattice parameters of the materials of adjacent oxide films either increase or decrease in size from one parameter to another parameter, a graded layup of films can be grown (with reduced strain levels therebetween) so that the outer film has a lattice parameter which closely approximates that of, and thus accomodates the epitaxial growth of, a pervoskite chosen to be grown upon the outer film.

  1. The Characterization of Eu2+-Doped Mixed Alkaline-Earth Iodide Scintillator Crystals

    SciTech Connect

    Neal, John S; Boatner, Lynn A; Ramey, Joanne Oxendine; Wisniewski, D.; Kolopus, James A; Cherepy, Nerine; Payne, Stephen A.

    2011-01-01

    The high-performance inorganic scintillator, SrI2:Eu2+, when activated with divalent europium in the concentration range of 3 to 6%, has shown great promise for use in applications that require high-energy-resolution gamma-ray detection. We have recently grown and tested crystals in which other alkaline-earth ions have been partially substituted for Sr ions. Specifically, europium-doped single crystals have been grown in which up to 30 at % of the strontium ions have been substituted for either by barium, magnesium, or calcium ions. In the case of the strontium iodide scintillator host, a material that is characterized by an orthorhombic crystal structure, there are three other column IIA elements that are obvious choices for investigations whose purpose is to realize potential improvements in the performance of SrI2:Eu2+-based scintillators via the replacement of strontium ions with either Mg2+, Ca2+, or Ba2+. Light yields of up to 81,400 photons/MeV with an associated energy resolution of 3.7% (fwhm for 662 keV gamma-rays) have been observed in the case of a partial substitution of Ba2+ for Sr2+. The measured decay times ranged from 1.1 to 2.0 s, while the peak emission wavelengths ranged from 432 to 438 nm.

  2. Alkaline earth silicate wools - A new generation of high temperature insulation.

    PubMed

    Brown, Robert C; Harrison, Paul T C

    2012-11-01

    Intensive study of the natural asbestiform minerals that cause human diseases, and the consequent understanding of their hazardous characteristics, has enabled the development of manufactured fibres whose physical and/or chemical properties, in particular as they relate to biopersistence, have been adjusted to minimize possible harm to health. A strong driver for the developmentof new high temperature insulation materials wasthe perception of the toxicity of refractory ceramic fibres (RCF)and their classification in the EU as a category 2 carcinogen under Directive 67/548/EEC. Such classification carries with it the requirement for substitution by less hazardous materials. This paper focuses on the development of alkaline earth silicate (AES) wools as a new class of high temperature insulation with the capability of such substitution in a number of applications. These wools have only a low potential to cause harm because they do not persist in lung tissue once deposited, and have produced minimal effects in experimental test systems. AES wools are increasingly being used in a wide range of high temperature applications.

  3. Mixed alkali effect on the spectroscopic properties of alkali-alkaline earth oxide borate glasses

    NASA Astrophysics Data System (ADS)

    Srinivas, G.; Ramesh, B.; Shareefuddin, Md.; Chary, M. N.; Sayanna, R.

    2016-05-01

    The mixed alkali and alkaline earth oxide borate glass with the composition xK2O - (25-x) Li2O-12.5BaO-12.5MgO-50B2O3 (x = 0, 5, 10, 15, 20 and 25mol %) and doped with 1mol% CuO were prepared by the melt quenching technique. From the optical absorption spectra the optical band gap, electronic polarizability(α02-), interaction parameter (A), theoretical and experimental optical basicity (Λ) values were evaluated. From the Electron Paramagnetic Resonance (EPR) spectral data the number of spins (N) and susceptibility (χ) were evaluated. The values of (α02-), and (Λ) increases with increasing of K2O content and electronic polarizability and interaction parameter show opposite behaviuor which may be due to the creation of non-bridging oxygens and expansion of borate network. The reciprocal of susceptibility (1/χ) and spin concentration (N) as a function of K2O content, varied nonlinearly which may be due to creation of non-bridging oxygens in the present glass system. This may be attributed to mixed alkali effect (MAE).

  4. Heavy water reactions with alkaline-earth metal dications in the gas phase

    NASA Astrophysics Data System (ADS)

    Feil, Stefan; Koyanagi, Greg K.; Bohme, Diethard K.

    2009-02-01

    Room temperature rate coefficients and product distributions are reported for the reactions initiated in D2O with dications of the alkaline-earth metals Mg, Ca, Sr and Ba. The measurements were performed with a selected-ion flow tube (SIFT) tandem mass spectrometer and electrospray ionization (ESI). Mg2+ reacts with water by a fast electron transfer leading to charge separation with a rate coefficient of 1.4 × 10-9 cm3 molecule-1 s-1. Ca2+ reacts with D2O in a first step to form the adduct Ca2+(D2O), with an effective bimolecular rate coefficient of 2.3 × 10-11 cm3 molecule-1 s-1, which then undergoes rapid charge separation by deuteron transfer to form CaOD+ and D3O+ in a second step with k = 7.9 × 10-10 cm3 molecule-1 s-1. The CaOD+ ion reacts further by clustering up to five more D2O molecules. Sr2+ clusters up to eight D2O molecules and Ba2+ up to seven D2O molecules, with the first addition of D2O being rate determining in each case and the last addition being distinctly slower, as might be expected from a transition in the occupation of the added water molecules from an inner to an outer hydration shell.

  5. Optimizing the performance of bandpass photon detectors for inverse photoemission: Transmission of alkaline earth fluoride window crystals

    SciTech Connect

    Thiede, Christian Schmidt, Anke B.; Donath, Markus

    2015-08-15

    Bandpass photon detectors are widely used in inverse photoemission in the isochromat mode at energies in the vacuum-ultraviolet spectral range. The energy bandpass of gas-filled counters is usually formed by the ionization threshold of the counting gas as high-pass filter and the transmission cutoff of an alkaline earth fluoride window as low-pass filter. The transmission characteristics of the window have, therefore, a crucial impact on the detector performance. We present transmission measurements in the vacuum-ultraviolet spectral range for alkaline earth fluoride window crystals in the vicinity of the transmission cutoff as a function of crystal purity, surface finish, surface contamination, temperature, and thickness. Our findings reveal that the transmission characteristics of the window crystal and, thus, the detector performance depend critically on these window parameters.

  6. The contents of alkali and alkaline earth metals in soils of the southern Cis-Ural region

    NASA Astrophysics Data System (ADS)

    Asylbaev, I. G.; Khabirov, I. K.

    2016-01-01

    The contents and distribution patterns of alkali and alkaline earth metals in soils and rocks of the southern Cis-Ural region were studied. A database on the contents of these metals was developed, the soils were classified with respect to their provision with these metals, and corresponding schematic maps showing their distribution in soils of the region were compiled. It was found that the contents of these metals decrease from east to west (from the Yuryuzan-Aisk Piedmont Plain to the Ufa Plateau and to the Belebeevsk Upland), and their distribution patterns change. Among alkali metals, the highest accumulation in the soils is typical of potassium, sodium, and cesium; among alkaline earth metals, of strontium and barium.

  7. Spin-Orbit-Coupled Correlated Metal Phase in Kondo Lattices: An Implementation with Alkaline-Earth Atoms

    NASA Astrophysics Data System (ADS)

    Isaev, L.; Schachenmayer, J.; Rey, A. M.

    2016-09-01

    We show that an interplay between quantum effects, strong on-site ferromagnetic exchange interaction, and antiferromagnetic correlations in Kondo lattices can give rise to an exotic spin-orbit coupled metallic state in regimes where classical treatments predict a trivial insulating behavior. This phenomenon can be simulated with ultracold alkaline-earth fermionic atoms subject to a laser-induced magnetic field by observing dynamics of spin-charge excitations in quench experiments.

  8. The etching process of boron nitride by alkali and alkaline earth fluorides under high pressure and high temperature

    SciTech Connect

    Guo, W.; Ma, H.A.; Jia, X.

    2014-03-01

    Graphical abstract: - Highlights: • Appropriate etch processes of hBN and cBN under HPHT are proposed. • The degree of the crystallization of hBN was decreased. • A special cBN growth mechanism with a triangular unit is proposed. • Plate-shape cBN crystals with large ratio of length to thickness were obtained. • A strategy provides useful guidance for controlling the cBN morphology. - Abstract: Some new etching processes of hexagonal boron nitride (hBN) and cubic boron nitride (cBN) under high pressure and high temperature in the presence of alkali and alkaline earth fluorides have been discussed. It is found that hBN is etched distinctly by alkali and alkaline earth fluorides and the morphology of hBN is significantly changed from plate-shape to spherical-shape. Based on the “graphitization index” values of hBN, the degree of the crystallization of hBN under high pressure and high temperature decreases in the sequence of LiF > CaF{sub 2} > MgF{sub 2}. This facilitates the formation of high-quality cBN single crystals. Different etch steps, pits, and islands are observed on cBN surface, showing the strong etching by alkali and alkaline earth fluorides and the tendency of layer-by-layer growth. A special layer growth mechanism of cBN with a triangular unit has been found. Furthermore, the morphologies of cBN crystals are apparently affected by a preferential surface etching of LiF, CaF{sub 2} and MgF{sub 2}. Respectively, the plate-shape and tetrahedral cBN crystals can be obtained in the presence of different alkali and alkaline earth fluorides.

  9. The MCVD synthesis and characterization of water tolerant fiber optic waveguides based on alkaline earth-doped silicas

    NASA Astrophysics Data System (ADS)

    Farley, Kevin F.

    Optical fibers that transmit throughout the entire telecommunications spectrum (1.2--1.7 mum) are presently manufactured by the removal of hydrogen or OH from the host preform glass. Hydrogen-oxygen torches are utilized in the conventional preform manufacturing process, but result in the formation of hydroxyls in germanium-doped silica fiber. The hydroxyl species generate unacceptably high losses for long haul telecommunications systems. This thesis has explored an alternative strategy for reducing OH-related absorption in silica-based glasses. Alkaline earth modifiers have been introduced via the modified chemical vapor deposition (MCVD) process to successfully damp out and dramatically reduce the extrinsic attenuation associated with both water and hydrogen. Specifically, alkaline earth ions were introduced into alumino-silicate glasses to form MgO-Al2O3-SiO2, CaO-Al 2O3-SiO2, and SrO-Al2O3-SiO 2 compositions. The utilization of halide precursors based on the vapor delivery of rare earths was incorporated into the existing MCVD set-up to fabricate these optical preforms. Both the bulk preforms and fibers drawn from them were characterized to determine relevant optical properties, including the attenuation, index profiles and extinction coefficients arising from OH in each host. The data indicate that modification of the silica glass structure through the additions of modifying ions can significantly reduce OH related absorption. For example, the doping of alkaline earth ions decreased the extinction coefficient measured at the 1.39 mum) OH overtone, to values < 0.2 L/(mol*cm). Prompt gamma activation analysis (PGAA) measurements conducted at the National Institute of Standards and Technology (NIST) found OH concentrations in the glasses in the range from 10 to 27.5 ppm. The alkaline earth-doped fibers exhibited lower OH absorption at 1.39 mum) than germanium and aluminum-doped reference fibers. Fibers doped with either magnesium, calcium or strontium displayed up

  10. 5 d-4 f luminescence of Nd3+, Gd3+, Er3+, Tm3+, and Ho3+ ions in crystals of alkaline earth fluorides

    NASA Astrophysics Data System (ADS)

    Radzhabov, E. A.; Prosekina, E. A.

    2011-09-01

    The vacuum ultraviolet emission spectra of alkaline-earth fluoride (CaF2, SrF2, BaF2) crystals with rare earth impurity ions (Nd, Gd, Er, Tm, Ho) have been investigated. The main luminescence bands are described well by the transitions from the lowest excited 5 d state to different 4 f levels of rare earth ions.

  11. Ocean-Based Alkalinity Enhancement: Mitigation Potential, Side Effects and the Fate of Added Alkalinity Assessed in an Earth System Model

    NASA Astrophysics Data System (ADS)

    Gonzalez, M. F.; Ilyina, T.

    2014-12-01

    Artificial ocean alkalinization (AOA) has been proposed as a mean to mitigate climate change and ocean acidification. Whilst the mitigation potential of this geo-engineering technology may sound promising, it poses environmental risks. Within the Priority Program "Climate Engineering" of the German Science Foundation (DFG), we investigate the mitigation potential of AOA to reduce atmospheric CO2 and counteract the consequences of ocean acidification. We are particularly interested in the residence time of the added alkalinity at the ocean surface because it must stay in the upper ocean in order to increase the oceanic CO2 uptake. The mitigation potential, risks and the unintended consequences of this geo-engineering method are also exhaustively studied. These questions are tackled through the analysis of different alkalinity enhancement scenarios in the state-of-the-art Earth system model of the Max Planck Institute for Meteorology (MPI-ESM) in a configuration based on the fifth phase of the Coupled Model Intercomparison Project (CMIP5). Model scenarios are designed so that AOA is performed to keep the atmospheric CO2 concentrations similar to values of the stabilization scenario RCP4.5, while fossil fuel CO2 emissions follow the pathway of the high-CO2 scenario RCP8.5. Alkalinity is added globally into the upper 12 meters of the ocean in different seasons and years. We found that on the time scale of relevance (i.e. from years to decades), season and location are key aspects to take into account in the implementation of AOA. This is because of inhomogeneous vertical mixing of added alkalinity due to the mixed layer depth which is established by the season. We also show that the rate of addition greatly determines impact and outcome of this geo-engineering method. Changes driven by the implementation of this method in the ocean biogeochemistry are also discussed. For instance, the associated changes in the carbon cycle, marine oxygen levels, saturation state of

  12. Novel alkaline earth copper germanates with ferro and antiferromagnetic S=1/2 chains

    SciTech Connect

    Brandao, Paula; Reis, Mario S; Gai, Zheng; Moreira Dos Santos, Antonio F

    2013-01-01

    Two new alkaline earth copper(II) germanates were hydrothermally synthesized: CaCuGeO4 center dot H2O (1) and BaCu2Ge3O9 center dot H2O (2), and their structures determined by single crystal X-ray diffraction. Compound (1) crystallizes in space group P2(1)/c with a=5.1320(2) angstrom, b=16.1637(5) angstrom, c=5.4818(2) angstrom, beta=102.609(2)degrees, V=443.76(3) angstrom(3) and Z=4. This copper germanate contains layers of composition [CuGeO4](infinity)(2-) comprising CuO4 square planes and GeO4 tetrahedra with calcium and water molecules in the inter-layer space. Compound (2) crystallizes in the Cmcm space group with a=5.5593(3) angstrom, b=10.8606(9) angstrom, c=13.5409(8) angstrom, V=817.56(9) angstrom(3) and Z=4. This structure contains GeO6 and CuO6 octahedra as well as GeO4 tetrahedra, forming a three-dimensional network of interconnecting six-membered ring channels. The magnetic susceptibility for both samples can be interpreted as S=1/2 chains, in agreement with the copper topology observed in the crystal structure. The susceptibility of (1) exhibits a Bonner-Fisher type behavior, resulting from antiferromagnetic intra-chain interactions without three-dimensional ordering down to 5 K-the lowest measured temperature. This observation, together with the absence of super-exchange paths between the copper chains, make this system particularly promising for the study of low dimensional magnetism. The magnetic properties of (2) show a very weak ferromagnetic near-neighbor interaction along the chain. In this compound a peak the chi T plot seems to indicate the onset of interchain antiferromagentic correlations. However, no ordering temperature is detected in the susceptibility data.

  13. Accumulation of alkaline earth metals by the green macroalga Bryopsis maxima.

    PubMed

    Takahashi, Shigekazu; Aizawa, Kyoko; Nakamura, Saki; Nakayama, Katsumi; Fujisaki, Shingo; Watanabe, Soichiro; Satoh, Hiroyuki

    2015-04-01

    Twenty-five days after the disaster at the Fukushima Daiichi nuclear power plant in 2011, we collected samples of the green macroalga Bryopsis maxima from the Pacific coast of Japan. Bryopsis maxima is a unicellular, multinuclear, siphonous green macroalga. Radiation analysis revealed that B. maxima emitted remarkably high gamma radiation of (131)I, (134)Cs, (137)Cs, and (140)Ba as fission products of (235)U. Interestingly, B. maxima contained naturally occurring radionuclides derived from (226)Ra and (228)Ra. Analysis of element content revealed that B. maxima accumulates many ocean elements, especially high quantities of the alkaline earth metals Sr (15.9 g per dry-kg) and Ba (3.79 g per dry-kg), whereas Ca content (12.5 g per dry-kg) was lower than that of Sr and only 61 % of the mean content of 70 Japanese seaweed species. Time-course analysis determined the rate of radioactive (85)Sr incorporation into thalli to be approximately 0.13 g Sr per dry-kg of thallus per day. Subcellular fractionation of B. maxima cells showed that most of the (85)Sr was localized in the soluble fraction, predominantly in the vacuole or cytosol. Given that (85)Sr radioactivity was permeable through a dialysis membrane, the (85)Sr was considered to be a form of inorganic ion and/or bound with a small molecule. Precipitation analysis with sodium sulfate showed that more than 70% of the Sr did not precipitate as SrSO4, indicating that a proportion of the Sr may bind with small molecules in B. maxima.

  14. Recent advances in tailoring the aggregation of heavier alkaline earth metal halides, alkoxides and aryloxides from non-aqueous solvents.

    PubMed

    Fromm, Katharina M

    2006-11-21

    This overview on one of the subjects treated in our group deals with the synthesis and study of low-dimensional polymer and molecular solid state structures formed with alkaline earth metal ions in non-aqueous solvents. We have chosen several synthetic approaches in order to obtain such compounds. The first concept deals with the "cutting out" of structural fragments from a solid state structure of a binary compound, which will be explained with reference to BaI2. Depending on the size and concentration of oxygen donor ligands, used as chemical scissors on BaI2, three-, two-, one- and zero-dimensional derived adducts of BaI2 are obtained, comparable to a structural genealogy tree for BaI2. A second part deals with the supramolecular approach for the synthesis of low dimensional polymeric compounds based on alkaline earth metal iodides, obtained by the combination of metal ion coordination with hydrogen bonding between the cationic complexes and their anions. Certain circumstances allow rules to be established for the prediction of the dimensionality of a given compound, contributing to the fundamental problem of structure prediction in crystal engineering. A third section describes a synthetic approach for generating pure alkaline earth metal cage compounds as well as alkali and alkaline earth mixed metal clusters. A first step deals with different molecular solvated alkaline earth metal iodides which are investigated as a function of the ligand size in non-aqueous solvents. These are then reacted with some alkali metal compound in order to partially or totally eliminate alkali iodide and to form the targeted clusters. These unique structures of ligand stabilized metal halide, hydroxide and/or alkoxide and aryloxide aggregates are of interest as potential precursors for oxide materials and as catalysts. Approaches to two synthetic methods of the latter, sol-gel and (MO)CVD (metal-organic chemical vapour deposition), are investigated with some of our compounds. (D

  15. (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.

  16. Electronic Principles of Some Trends in Properties of Metallic Hydrides

    NASA Astrophysics Data System (ADS)

    Ivanović, Nenad; Novaković, Nikola; Colognesi, Daniele; Radisavljević, Ivana; Ostojić, Stanko

    Due to their extensive present, important and versatile potential applications, metal hydrides (MH) are among the most investigated solid-state systems. Theoretical, numerical and experimental studies have provided a considerable knowledge about their structure and properties, but in spite of that, the basic electronic principles of various interactions present in MH have not yet been completely resolved. Even in the simplest MH, i.e. alkali hydrides (Alk-H), some trends in physical properties, and especially their deviations, are not well understood. Similar doubts exist for the alkaline-earth hydride (AlkE-H) series, and are even more pronounced for complex systems, like transition metal-doped AlkE-H, alanates and borohydrides. This work is an attempt of explaining some trends in the physical properties of Alk-H and AlkE-H, employing the Bader analysis of the charge distribution topology evaluated by first-principle all-electron calculations. These results are related to some variables commonly used in the explanation of experimental and calculated results, and are also accompanied by simple tight-binding estimations. Such an approach provides a valuable insight in the characteristics of M-H and H-H interactions in these hydrides, and their possible changes along with external parameters, like temperature, pressure, defect or impurity introduction. The knowledge of these basic interactions and processes taking place in simple MH are essential for the design and optimisation of complex MH-systems interesting for practical hydrogen storage applications.

  17. ION EXCHANGE IN FUSED SALTS. II. THE DISTRIBUTION OF ALKALI METAL AND ALKALINE EARTH IONS BETWEEN CHABAZITE AND FUSED LINO3, NANO3, AND KNO3,

    DTIC Science & Technology

    ION EXCHANGE, SALTS ), (*ALKALI METALS, ION EXCHANGE), (*ALKALINE EARTH METALS, ION EXCHANGE), (*NITRATES, ION EXCHANGE), SODIUM , CALCIUM, POTASSIUM...BARIUM, RUBIDIUM, CESIUM, LITHIUM COMPOUNDS, SODIUM COMPOUNDS, POTASSIUM COMPOUNDS, DISTRIBUTION, MINERALS, IONS

  18. [Effect of bivalent alkaline earth fluorides introduction on thermal stability and spectroscopic properties of Er3+/Tm3+ /Yb3+ co-doped oxyfluorogermanate glasses].

    PubMed

    Hu, Yue-bo; Zhang, Xin-na; Zhou, Da-li; Jiao, Qing; Wang, Rong-fei; Huang, Jin-feng; Long, Xiao-bo; Qiu, Jian-bei

    2012-01-01

    Transparent Er3+/Tm3+ /Yb3+ co-doped oxyfluorogermanate glasses alone containing MgF2, CaF2, SrF2 or BaF2 and nano-glass-ceramics only containing BaF2 were prepared. The thermal stabilities and the up-conversion emission properties of the samples were investigated. Analyses of absorbance spectra reveal that the UV cutoff band moves slightly to shortwave band with the doping bivalent cation mass increasing. The results show that the emission color can be adjusted by changing the alkaline earth cation species in the glass matrixes, especially as Mg2+ is concerned, and the emission intensity can increase notably by heating the glass containing alkaline-earth fluoride into glass ceramic containing alkaline-earth fluoride nanocrystals or increasing the content of bivalent alkaline earth fluorides.

  19. Monte Carlo simulations of electron thermalization in alkali iodide and alkaline-earth fluoride scintillators

    NASA Astrophysics Data System (ADS)

    Wang, Zhiguo; Xie, YuLong; Campbell, Luke W.; Gao, Fei; Kerisit, Sebastien

    2012-07-01

    A Monte Carlo model of electron thermalization in inorganic scintillators, which was developed and applied to CsI in a previous publication [Wang et al., J. Appl. Phys. 110, 064903 (2011)], is extended to another material of the alkali halide class, NaI, and to two materials from the alkaline-earth halide class, CaF2 and BaF2. This model includes electron scattering with both longitudinal optical (LO) and acoustic phonons as well as the effects of internal electric fields. For the four pure materials, a significant fraction of the electrons recombine with self-trapped holes and the thermalization distance distributions of the electrons that do not recombine peak between approximately 25 and 50 nm and extend up to a few hundreds of nanometers. The thermalization time distributions of CaF2, BaF2, NaI, and CsI extend to approximately 0.5, 1, 2, and 7 ps, respectively. The simulations show that the LO phonon energy is a key factor that affects the electron thermalization process. Indeed, the higher the LO phonon energy is, the shorter the thermalization time and distance are. The thermalization time and distance distributions show no dependence on the incident γ-ray energy. The four materials also show different extents of electron-hole pair recombination due mostly to differences in their electron mean free paths (MFPs), LO phonon energies, initial densities of electron-hole pairs, and static dielectric constants. The effect of thallium doping is also investigated for CsI and NaI as these materials are often doped with activators. Comparison between CsI and NaI shows that both the larger size of Cs+ relative to Na+, i.e., the greater atomic density of NaI, and the longer electron mean free path in NaI compared to CsI contribute to an increased probability for electron trapping at Tl sites in NaI versus CsI.

  20. Influence of doping with alkaline earth metals on the optical properties of thermochromic VO2

    NASA Astrophysics Data System (ADS)

    Dietrich, Marc K.; Kramm, Benedikt G.; Becker, Martin; Meyer, Bruno K.; Polity, Angelika; Klar, Peter J.

    2015-05-01

    Thin films of doped VO2 were deposited, analyzed, and optimized with regard to their solar energy transmittance (Tsol) and visible/luminous light transmittance (Tlum) which are important parameters in the context of smart window applications in buildings. The doping with alkaline earth metals (AEM) like Mg, Ca, Sr, or Ba increased both Tsol and Tlum due to a bandgap widening and an associated absorption edge blue-shift. Thereby, the brown-yellowish color impression of pure VO2 thin films, which is one major hindrance limiting the usage of VO2 as thermochromic window coating, was overcome. Transparent thin films with excellent switching behavior were prepared by sputtering. Highly doped V1-xMexO2 (Me = Ca, Sr, Ba) kept its excellent thermochromic switching behavior up to x(Me) = Me/(Me + V) = 10 at. % doping level, while the optical bandgap energy was increased from 1.64 eV for undoped VO2 to 2.38 eV for x(Mg) = 7.7 at. %, 1.85 eV for x(Ca) = 7.4 at. %, 1.84 eV for x(Sr) = 6.4 at. % and 1.70 eV for x(Ba) = 6.8 at. %, as well as the absorption edge is blue shifted by increasing AEM contents. Also, the critical temperature ϑc, at which the semiconductor-to-metal transition (SMT) occurs, was decreased by AEM doping, which amounted to about -0.5 K/at. % for all AEM on average. The critical temperature was determined by transmittance-temperature hysteresis measurements. Furthermore, Tsol and Tlum were calculated and were found to be significantly enhanced by AEM doping. Tlum increased from 32.0% in undoped VO2 to 43.4% in VO2 doped with 6.4 at. % Sr. Similar improvements were found for other AEM. The modulation of the solar energy transmittance ΔTsol, which is the difference of the Tsol values in the low and high temperature phase, was almost constant or even slightly increased when the doping level was increased up to about 10 at. % Ca, Sr, or Ba.

  1. Overview of the crystal chemistry of the actinide chalcogenides: incorporation of the alkaline-earth elements.

    PubMed

    Mesbah, Adel; Prakash, Jai; Ibers, James A

    2016-10-18

    This review focuses on the results of exploratory syntheses of alkaline-earth-metal actinide chalcogenides Ak-An-Q (Ak = Ba, Sr; An = Th, U; Q = S, Se, and Te). About thirty new compounds are described. Although the basic building blocks of their structures are usually AnQ6 octahedra and AkQ8 bicapped trigonal prisms, these are combined in diverse ways to afford eleven new structure types. The structures reconfirm the prevailing presence of An(4+) in chalcogenides, although some of the compounds discovered are mixed An(4+)/An(5+) systems, and a few contain only An(5+). The tendency of the chalcogens to form Q-Q bonds is again evident from the presence of S-S single bonds and infinite Te-Te-Te linear chains. The latter possess interatomic distances of lengths greater than that of a Te-Te single bond but less than that of a Te-Te van der Waals interaction. Assignment of formal oxidation states in compounds containing these chains is arbitrary at best. Addition of metal atoms (M) affords quaternary structures, some of which show remarkable flexibility in the positions of the An and M atoms, and in such compounds the nature of the M elements influences directly the dimensionality of the resultant structure. The presence of adventitious oxygen, often from etching of the fused-silica tubes by oxyphilic An elements, results in new quintary compounds that show remarkable structural variations with change of M. The compounds discussed have shown transport and electronic structures that range from metallic-like to semiconducting. We find, with the exception of BaUSe3, when comparisons can be made that the values of the calculated band gaps are reasonably close but usually lower than the experimentally derived values. Thus the method used, in particular the HSE functional, has been generally successful on these 5f actinides. This is an important result because in the absence of suitable crystals, and hence experimental measurements, it still may be possible to offer credible

  2. Monte Carlo simulations of electron thermalization in alkali iodide and alkaline-earth fluoride scintillators

    SciTech Connect

    Wang Zhiguo; Gao Fei; Kerisit, Sebastien; Xie Yulong; Campbell, Luke W.

    2012-07-01

    A Monte Carlo model of electron thermalization in inorganic scintillators, which was developed and applied to CsI in a previous publication [Wang et al., J. Appl. Phys. 110, 064903 (2011)], is extended to another material of the alkali halide class, NaI, and to two materials from the alkaline-earth halide class, CaF{sub 2} and BaF{sub 2}. This model includes electron scattering with both longitudinal optical (LO) and acoustic phonons as well as the effects of internal electric fields. For the four pure materials, a significant fraction of the electrons recombine with self-trapped holes and the thermalization distance distributions of the electrons that do not recombine peak between approximately 25 and 50 nm and extend up to a few hundreds of nanometers. The thermalization time distributions of CaF{sub 2}, BaF{sub 2}, NaI, and CsI extend to approximately 0.5, 1, 2, and 7 ps, respectively. The simulations show that the LO phonon energy is a key factor that affects the electron thermalization process. Indeed, the higher the LO phonon energy is, the shorter the thermalization time and distance are. The thermalization time and distance distributions show no dependence on the incident {gamma}-ray energy. The four materials also show different extents of electron-hole pair recombination due mostly to differences in their electron mean free paths (MFPs), LO phonon energies, initial densities of electron-hole pairs, and static dielectric constants. The effect of thallium doping is also investigated for CsI and NaI as these materials are often doped with activators. Comparison between CsI and NaI shows that both the larger size of Cs{sup +} relative to Na{sup +}, i.e., the greater atomic density of NaI, and the longer electron mean free path in NaI compared to CsI contribute to an increased probability for electron trapping at Tl sites in NaI versus CsI.

  3. Unified mechanism of alkali and alkaline earth catalyzed gasification reactions of carbon by CO2 and H2O

    USGS Publications Warehouse

    Chen, S.G.; Yang, R.T.

    1997-01-01

    From molecular orbital calculations, a unified mechanism is proposed for the gasification reactions of graphite by CO2 and H2O, both uncatalyzed and catalyzed by alkali and alkaline earth catalysts. In this mechanism, there are two types of oxygen intermediates that are bonded to the active edge carbon atoms: an in-plane semiquinone type, Cf(O), and an off-plane oxygen bonded to two saturated carbon atoms that are adjacent to the semiquinone species, C(O)Cf(O). The rate-limiting step is the decomposition of these intermediates by breaking the C-C bonds that are connected to Cf(O). A new rate equation is derived for the uncatalyzed reactions, and that for the catalyzed reactions is readily available from the proposed mechanism. The proposed mechanism can account for several unresolved experimental observations: TPD and TK (transient kinetics) desorption results of the catalyzed systems, the similar activation energies for the uncatalyzed and catalyzed reactions, and the relative activities of the alkali and alkaline earth elements. The net charge of the edge carbon active site is substantially changed by gaining electron density from the alkali or alkaline earth element (by forming C-O-M, where M stands for metal). The relative catalytic activities of these elements can be correlated with their abilities of donating electrons and changing the net charge of the edge carbon atom. As shown previously (Chen, S. G.; Yang, R. T. J. Catal. 1993, 141, 102), only clusters of the alkali compounds are active. This derives from the ability of the clusters to dissociate CO2 and H2O to form O atoms and the mobility of the dissociated O atoms facilitated by the clusters.

  4. 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.

  5. 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.

  6. Tris(pyrazolyl)methanides of the alkaline earth metals: influence of the substitution pattern on stability and degradation.

    PubMed

    Müller, Christoph; Koch, Alexander; Görls, Helmar; Krieck, Sven; Westerhausen, Matthias

    2015-01-20

    Trispyrazolylmethanides commonly act as strong tridentate bases toward metal ions. This expected coordination behavior has been observed for tris(3,4,5-trimethylpyrazolyl)methane (1a), which yields the alkaline-earth-metal bis[tris(3,4,5-trimethylpyrazolyl)methanides] of magnesium (1b), calcium (1c), strontium (1d), and barium (1e) via deprotonation of 1a with dibutylmagnesium and [Ae{N(SiMe3)2}2] (Ae = Mg, Ca, Sr, and Ba, respectively). Barium complex 1e degrades during recrystallization that was attempted from aromatic hydrocarbons and ethers. In these scorpionate complexes, the metal ions are embedded in distorted octahedral coordination spheres. Contrarily, tris(3-thienylpyrazolyl)methane (2a) exhibits a strikingly different reactivity. Dibutylmagnesium is unable to deprotonate 2a, whereas [Ae{N(SiMe3)2}2] (Ae = Ca, Sr, and Ba) smoothly metalates 2a. However, the primary alkaline-earth-metal bis[tris(3-thienylpyrazolyl)methanides] of Ca (2c), Sr (2d), and Ba (2e) represent intermediates and degrade under the formation of the alkaline-earth-metal bis(3-thienylpyrazolates) of calcium (3c), strontium (3d), and barium (3e) and the elimination of tetrakis(3-thienylpyrazolyl)ethene (4). To isolate crystalline compounds, 3-thienylpyrazole has been metalated, and the corresponding derivatives [(HPz(Tp))4Mg(Pz(Tp))2] (3b), dinuclear [(tmeda)Ca(Pz(Tp))2]2 (3c), mononuclear [(pmdeta)Sr(Pz(Tp))2] (3d), and [(hmteta)Ba(Pz(Tp))2] (3e) have been structurally characterized. Regardless of the applied stoichiometry, magnesiation of thienylpyrazole 3a with dibutylmagnesium yields [(HPz(Tp))4Mg(Pz(Tp))2] (3b), which is stabilized in the solid state by intramolecular N-H···N···H-N hydrogen bridges. The degradation of [Ae{C(Pz(R))3}2] (R = Ph and Tp) has been studied by quantum chemical methods, the results of which propose an intermediate complex of the nature [{(Pz(R))2C}2Ca{Pz(R)}2]; thereafter, the singlet carbenes ([:C(Pz(R))2]) dimerize in the vicinity of the alkaline

  7. The effect of alkaline earth metal ion dopants on photocatalytic water splitting by NaTaO(3) powder.

    PubMed

    Iwase, Akihide; Kato, Hideki; Kudo, Akihiko

    2009-01-01

    Alkaline earth metal ions (Ca, Sr, and Ba) are doped into a NaTaO(3) photocatalyst, yielding fine particles and surface structures with nanometer-scale "steps." The formation of the surface nanostep structure depends on the amount of doped Sr and Ba. The photocatalytic water splitting over NaTaO(3) is enhanced: NaTaO(3) doped with 0.5 and 1.0 mol % of Sr shows high activities for photocatalytic water splitting without loading of a co-catalyst, and the photocatalytic activity is further improved by loading with a NiO co-catalyst.

  8. Luminescence properties of Eu-activated alkaline and alkaline-earth silicate Na{sub 2}Ca{sub 3}Si{sub 6}O{sub 16}

    SciTech Connect

    Wang, Jing; Huang, Yanlin; Wang, Xigang; Qin, Lin; Seo, Hyo Jin

    2014-07-01

    Highlights: • A novel yellow-emitting alkaline and alkaline-earth silicate Na{sub 2}Ca{sub 3}Si{sub 6}O{sub 16}:Eu{sup 2+} was first developed. • Under excitation with UV or near UV light the silicate presents broad emission band centered at 580 nm. - Abstract: Yellow-emitting phosphors of Na{sub 2}Ca{sub 3}Si{sub 6}O{sub 16}:Eu{sup 2+} was prepared by wet chemistry sol–gel method. X-ray powder diffraction and SEM measurements were applied to characterize the structure and morphology, respectively. The luminescence properties were investigated by the photoluminescence excitation and emission spectra, decay curve (lifetimes), CIE coordinates and the internal quantum efficiencies. The excitation spectra can match well with the emission light of near UV-LED chips (360–400 nm). Na{sub 2}Ca{sub 3}Si{sub 6}O{sub 16}:Eu{sup 2+} presents a symmetric emission band from 4f{sup 6}5d{sup 1} ⟶ 4f{sup 7}({sup 8}S{sub 7/2}) transitions of Eu{sup 2+} ions on doping below 3.0 mol%. On increasing Eu-doping levels, the sample contains two kinds of emission centers, i.e., Eu{sup 2+} and Eu{sup 3+} ions, which present the characteristic broad band (5d ⟶ 4f) and narrower (4f ⟶ 4f) luminescence lines, respectively. The energy transfer, the luminescence thermal stability (activation energy ΔE for thermal quenching) and luminescence mechanism of Na{sub 2}Ca{sub 3}Si{sub 6}O{sub 16}:Eu{sup 2+} phosphors were discussed by analyzing the relationship between the luminescence characteristics and the crystal structure.

  9. Synthesis and Characterization of Alkaline-Earth Metal (Ca, Sr, and Ba) Doped Nanodimensional LaMnO3 Rare-Earth Manganites

    NASA Astrophysics Data System (ADS)

    Asma, Khalid; Saadat, Anwar Siddiqi; Affia, Aslam

    2013-07-01

    The substitution of divalent cations of alkaline-earth elements in nanodimensional structures of rare-earth manganites produces advanced materials with potential electrical and magnetic functionalities. A systematic investigation of La0.65A0.35MnO3 (A = Ca, Sr, Ba) materials synthesized with a modified citrate route adopting ethanol dehydration has been undertaken. The structural and morphological analyses are carried out by using x-ray diffraction and scanning electron microscopy, respectively. Resistivity measurements are performed in variation with temperature to study the electrical transport properties which are found to vary with the size of the A-site cationic radius. Room temperature magnetic measurements are carried out to investigate the type of magnetic phase present in materials. The stability of the magnetic phase and coercivity are found to be dependent on the size of nanocrystallites.

  10. Thermodynamic stability of perovskites and related compounds in some alkaline earth-transition metal-oxygen systems

    NASA Astrophysics Data System (ADS)

    Yokokawa, Harumi; Sakai, Natsuko; Kawada, Tatsuya; Dokiya, Masayuki

    1991-09-01

    The thermodynamic properties of some alkaline earth ( A)-transition metal ( M) perovskites and K 2NiF 4 compounds have been collected, analyzed, and utilized to examine their stabilities by constructing the chemical potential diagrams of a log [ {a(A)}/{a(M)}] vs log P(O 2) plot. A thermodynamic analysis was performed on the dissociation reaction of K 2NiF 4 compounds ( A2MO 4) into perovskites ( AMO 3) and alkaline earth oxides ( AO) using empirical correlations between stabilization energy and tolerance factor. It has been found that the softness of calcium ions, which shrink markedly with decreasing coordination number from 12 to 9, makes the calcium K 2NiF 4 compounds (Ca 2MO 4) relatively less stable with increasing radius of the transition metal ions, r( M4+). This destabilization related to the coordination-number-dependent radii implies that when compared with the strontium perovskites, the calcium analogous perovskites may have a smaller number of oxygen vacancies, because the formation of oxygen vacancies should be accompanied with a decrease in coordination number of A-site ions.

  11. Binding and selectivity of phenazino-18-crown-6-ether with alkali, alkaline earth and toxic metal species: A DFT study

    NASA Astrophysics Data System (ADS)

    Islam, Nasarul; Chimni, Swapandeep Singh

    2017-02-01

    The interactions of phenazino-crown ether ligands with alkali, alkaline earth and selected toxic species were investigated using density functional theory modelling by employing B3PW91/6-311G ++ (d, p) level of theory. The complex stability was analysed in terms of binding energies, perturbation energies, position of highest molecular orbital and energy gap values. In general, the complexes formed by P18C6-1a ligand with metal cations were found to be more stable than those with P18C6-1b. Among alkali and alkaline earth metals complexes having highest stability was observed for the complex formed by P18C6-1a with Be2+. Computational calculations of P18C6 ligand with toxic metal ions reveals that the P18C6-Cr6+ metal complexes acquire envelop like geometry, leading to higher binding energy values. Comparing the binding energies of neutral and monocations of Ag and Hg, the former had higher value both in neutral as well as monocation state. Thus, the stability of metal complexes is determined not only by the ligand but also by the type of metal ion. In solvent systems the stability constants of metal complexes were found increasing with decreasing permittivity of the solvent. This reflects the inherited polar character of the protic solvents stabilises the cation, resulting in decrease of effective interaction of ligand with the metal ion.

  12. Three interesting coordination compounds based on metalloligand and alkaline-earth ions: Syntheses, structures, thermal behaviors and magnetic property

    NASA Astrophysics Data System (ADS)

    Zhou, Qiang; Qian, Jun; Zhang, Chi

    2016-09-01

    Based on metalloligand LCu ([Cu(2,4-pydca)2]2-, 2,4-pydca2- = pyridine-2,4-dicarboxylate) and alkaline-earth ions (Ca2+, Sr2+, and Ba2+), three interesting coordination compounds, [Ca(H2O)7][LCu·H2O]·H2O (1), {Sr[LCu·H2O]·4H2O}n (2), and {Ba[LCu·H2O]·8H2O}n (3), have been synthesized and well-characterized by elemental analysis, infrared spectroscopy, thermogravimetric and single-crystal X-ray diffraction analysis. X-ray crystallographic studies reveal that 1 features a discrete 0D coordination compound, while 2 and 3 exhibit the 2D network and 1D chain structures, respectively. Compound 2 is constructed from {LCu}2 dimers connected with {Sr2} units, which is fabricated by two Sr2+ ions bridged via two μ2-O bridges, while compound 3 is formed by 1D {Ba}n chain linked with metalloligands LCu and exhibits an interesting sandwich like chain structure. It is noted that the coordination numbers of alkaline-earth ions are in positive correlation with their radiuses. Moreover, the magnetic property of compound 2 has been studied.

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

    NASA Astrophysics Data System (ADS)

    Settouti, Nadera; Aourag, Hafid

    2016-08-01

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

  14. Hydride development for hydrogen storage

    SciTech Connect

    Thomas, G.J.; Guthrie, S.E.; Bauer, W.; Yang, N.Y.C.; Sandrock, G.

    1996-10-01

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

  15. Oxidation behavior of Cr(III) during thermal treatment of chromium hydroxide in the presence of alkali and alkaline earth metal chlorides.

    PubMed

    Mao, Linqiang; Gao, Bingying; Deng, Ning; Liu, Lu; Cui, Hao

    2016-02-01

    The oxidation behavior of Cr(III) during the thermal treatment of chromium hydroxide in the presence of alkali and alkaline earth metal chlorides (NaCl, KCl, MgCl2, and CaCl2) was investigated. The amounts of Cr(III) oxidized at various temperatures and heating times were determined, and the Cr-containing species in the residues were characterized. During the transformation of chromium hydroxide to Cr2O3 at 300 °C approximately 5% of the Cr(III) was oxidized to form intermediate compounds containing Cr(VI) (i.e., CrO3), but these intermediates were reduced to Cr2O3 when the temperature was above 400 °C. Alkali and alkaline earth metals significantly promoted the oxidation of Cr(III) during the thermal drying process. Two pathways were involved in the influences the alkali and alkaline earth metals had on the formation of Cr(VI). In pathway I, the alkali and alkaline earth metals were found to act as electron transfer agents and to interfere with the dehydration process, causing more intermediate Cr(VI)-containing compounds (which were identified as being CrO3 and Cr5O12) to be formed. The reduction of intermediate compounds to Cr2O3 was also found to be hindered in pathway I. In pathway II, the alkali and alkaline earth metals were found to contribute to the oxidation of Cr(III) to form chromates. The results showed that the presence of alkali and alkaline earth metals significantly increases the degree to which Cr(III) is oxidized during the thermal drying of chromium-containing sludge.

  16. Half metallic ferromagnetism in alkaline-earth metal nitrides XN (X=Ca, Sr and Ba): A first principles study

    NASA Astrophysics Data System (ADS)

    Palanichamy, R. Rajeswara; Priyanga, G. Sudha; Cinthia, A. Jemmy; Murugan, A.; Meenaatci, A. T. Asvini; Iyakutti, K.

    2013-11-01

    The structural, electronic, mechanical and magnetic properties of 3 alkaline-earth metal nitrides (XN: X=Ca, Sr, and Ba) are investigated by the first principles calculations based on density functional theory using the Vienna ab-initio simulation code. At ambient pressure all the 3 nitrides are stable in the ferromagnetic state with a cubic NaCl structure. The calculated lattice parameters are in good agreement with the available results. The electronic structure reveals that these materials are half metallic ferromagnets at normal pressure. A pressure-induced structural phase transition from NaCl (B1) to CsCl (B2) phase is observed in CaN, SrN and BaN. On further increasing the pressure, a half metallic to metallic transition is also observed in these nitrides. Ferromagnetism is quenched in all the 3 nitrides at high pressures.

  17. Two-band superfluidity and intrinsic Josephson effect in alkaline-earth-metal Fermi gases across an orbital Feshbach resonance

    NASA Astrophysics Data System (ADS)

    Iskin, M.

    2016-07-01

    We first show that the many-body Hamiltonian governing the physical properties of an alkaline-earth 173Yb Fermi gas across the recently realized orbital Feshbach resonance is exactly analogous to that of two-band s -wave superconductors with contact interactions; i.e., even though the free-particle bands have a tunable energy offset in between and are coupled by a Josephson-type attractive interband pair scattering, the intraband interactions have exactly the same strength. We then introduce two intraband order parameters within the BCS mean-field approximation and investigate the competition between their in-phase and out-of-phase (i.e., the so-called π -phase) solutions in the entire BCS-BEC evolution at zero temperature.

  18. High-T sub c thin films on low microwave loss alkaline-rare-earth-aluminate crystals

    SciTech Connect

    Sobolewski, R.; Gierlowski, P.; Kula, W.; Zarembinski, S.; Lewandowski, S.J.; Berkowski, M.; Pajaczkowska, A. ); Gorshunov, B.P.; Lyudmirsky, D.B.; Sirotinsky, O.I. )

    1991-03-01

    This paper reports on the alkaline-rare-earth aluminates (K{sub 2}NiF{sub 4}-type perovskites) which are an excellent choice as the substrate material for the growth of high-T{sub c} thin films suitable for microwave and far-infrared applications. The CaNdAlO{sub 4}, and SrLaAlO{sub 4} single crystals have been grown by Czochralski pulling and fabricated into the form of (001) oriented wafers. The Y-Ba-Cu-O and Bi-Sr-Ca-Cu-O films deposited on these substrates by a single-target magnetron sputtering exhibited very good superconducting and structural properties.

  19. Cyclotron dynamics of a Kondo singlet in a spin-orbit-coupled alkaline-earth-metal atomic gas

    NASA Astrophysics Data System (ADS)

    Jiang, Bo-Nan; Lv, Hao; Wang, Wen-Li; Du, Juan; Qian, Jun; Wang, Yu-Zhu

    2014-11-01

    We propose a scheme to investigate the interplay between the Kondo-exchange interaction and the quantum spin Hall effect with ultracold fermionic alkaline-earth-metal atoms trapped in two-dimensional optical lattices using ultracold collision and laser-assisted tunneling. In the strong Kondo-coupling regime, although the loop trajectory of the mobile atom disappears, collective dynamics of an atom pair in two clock states can exhibit an unexpected spin-dependent cyclotron orbit in a plaquette, realizing the quantum spin Hall effect of the Kondo singlet. We demonstrate that the collective cyclotron dynamics of the spin-zero Kondo singlet is governed by an effective Harper-Hofstadter model in addition to second-order diagonal tunneling.

  20. Physical and optical absorption studies of Fe3+ - ions doped lithium borate glasses containing certain alkaline earths

    NASA Astrophysics Data System (ADS)

    Bhogi, Ashok; Kumar, R. Vijaya; Kistaiah, P.

    2016-05-01

    Iron ion doped lithium borate glasses with the composition 15RO-25Li2O-59B2O3-1Fe2O3 (where R= Ca, Sr and Ba) have been prepared by the conventional melt quenching technique and characterized to investigate the physical and optical properties using XRD, density, molar volume and UV-Visible spectroscopy. The optical absorption spectra exhibit a band at around 460 nm which is assigned to 6A1g(S) → 4Eg (G) of Fe3+ ions with distorted octahedral symmetry. From ultraviolet absorption edges, the optical band gap and Urbach energies have been evaluated. The effect of alkaline earths on these properties is discussed.

  1. Alkaline earth lead and tin compounds Ae2Pb, Ae2Sn, Ae = Ca, Sr, Ba, as thermoelectric materials.

    PubMed

    Parker, David; Singh, David J

    2013-10-01

    We present a detailed theoretical study of three alkaline earth compounds Ca2Pb, Sr2Pb and Ba2Pb, which have undergone little previous study, calculating electronic band structures and Boltzmann transport and bulk moduli using density functional theory. We also study the corresponding tin compounds Ca2Sn, Sr2Sn and Ba2Sn. We find that these are all narrow band gap semiconductors with an electronic structure favorable for thermoelectric performance, with substantial thermopowers for the lead compounds at temperature ranges from 300 to 800 K. For the lead compounds, we further find very low calculated bulk moduli-roughly half of the values for the lead chalcogenides, suggestive of soft phonons and hence low lattice thermal conductivity. All these facts indicate that these materials merit experimental investigation as potential high performance thermoelectrics. We find good potential for thermoelectric performance in the environmentally friendly stannide materials, particularly at high temperature.

  2. Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite for methanol synthesis

    DOEpatents

    Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

    1993-01-01

    The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

  3. Dispersion coefficients for H and He interactions with alkali-metal and alkaline-earth-metal atoms

    SciTech Connect

    Mitroy, J.; Bromley, M.W.J.

    2003-12-01

    The van der Waals coefficients C{sub 6}, C{sub 8}, and C{sub 10} for H and He interactions with the alkali-metal (Li, Na, K, and Rb) and alkaline-earth-metal (Be, Mg, Ca, and Sr) atoms are determined from oscillator strength sum rules. The oscillator strengths were computed using a combination of ab initio and semiempirical methods. The dispersion parameters generally agree with close to exact variational calculations for Li-H and Li-He at the 0.1% level of accuracy. For larger systems, there is agreement with relativistic many-body perturbation theory estimates of C{sub 6} at the 1% level. These validations for selected systems attest to the reliability of the present dispersion parameters. About half the present parameters lie within the recommended bounds of the Standard and Certain compilation [J. Chem. Phys. 83, 3002 (1985)].

  4. Alkaline earth lead and tin compounds Ae2Pb, Ae2Sn, Ae=Ca,Sr,Ba, as thermoelectric materials

    SciTech Connect

    Parker, David S; Singh, David J

    2013-01-01

    We present a detailed theoretical study of three alkaline earth compounds Ca2Pb, Sr2Pb and Ba2Pb, which have undergone little previous study, calculating electronic band structures and Boltzmann transport and bulk moduli using density functional theory. We also study the corresponding tin compounds Ca2 Sn, Sr2 Sn and Ba2 Sn. We find that these are all narrow band gap semiconductors with an electronic structure favorable for thermoelectric performance, with substantial thermopowers for the lead compounds at temperature ranges from 300 to 800 K. For the lead compounds, we further find very low calculated bulk moduli - roughly half of the values for the lead chalcogenides, suggestive of soft phonons and hence low lattice thermal conductivity. All these facts indicate that these materials merit experimental investigation as potential high performance thermoelectrics. We find good potential for thermoelectric performance in the environmentally friendly stannide materials, particularly at high temperature.

  5. Heteroleptic alkyl and amide iminoanilide alkaline earth and divalent rare earth complexes for the catalysis of hydrophosphination and (cyclo)hydroamination reactions.

    PubMed

    Liu, Bo; Roisnel, Thierry; Carpentier, Jean-François; Sarazin, Yann

    2013-09-27

    [{N^N}M(X)(thf)n] alkyl (X=CH(SiMe3)2) and amide (X=N(SiMe3)2) complexes of alkaline earths (M=Ca, Sr, Ba) and divalent rare earths (Yb(II) and Eu(II) ) bearing an iminoanilide ligand ({N^N}(-)) are presented. Remarkably, these complexes proved to be kinetically stable in solution. X-ray diffraction studies allowed us to establish size-structure trends. Except for one case of oxidation with [{N^N}Yb(II){N(SiMe3)2}(thf)], all these complexes are stable under the catalytic conditions and constitute effective precatalysts for the cyclohydroamination of terminal aminoalkenes and the intermolecular hydroamination and intermolecular hydrophosphination of activated alkenes. Metals with equal sizes across alkaline earth and rare earth families display almost identical apparent catalytic activity and selectivity. Hydrocarbyl complexes are much better catalyst precursors than their amido analogues. In the case of cyclohydroamination, the apparent activity decreases with metal size: Ca>Sr>Ba, and the kinetic rate law agrees with R(CHA) =k[precatalyst](1)[aminoalkene](1). The intermolecular hydroamination and hydrophosphination of styrene are anti-Markovnikov regiospecific. In both cases, the apparent activity increases with the ionic radius (Ca

  6. EPR and optical absorption studies of Cu{sup 2+} ions in alkaline earth alumino borate glasses

    SciTech Connect

    Ramesh Kumar, V.; Rao, J.L. . E-mail: jlrao46@yahoo.co.in; Gopal, N.O.

    2005-08-11

    Electron paramagnetic resonance (EPR) and optical absorption spectra of Cu{sup 2+} ions in alkaline earth alumino borate glasses doped with different concentrations of CuO have been studied. The EPR spectra of all the glasses exhibit the resonance signals, characteristic of Cu{sup 2+} ions present in axially elongated octahedral sites. The number of spins participating in the resonance has been calculated as a function of temperature for calcium alumino borate (CaAB) glass doped with 0.1 mol% of CuO. From the EPR data, the paramagnetic susceptibility ({chi}) was calculated at different temperatures (T) and from the 1/{chi}-T graph, the Curie temperature of the glass has been evaluated. The optical absorption spectra of all the glasses show a single broad band, which has been assigned to the {sup 2}B{sub 1g} {yields} {sup 2}B{sub 2g} transition of the Cu{sup 2+} ions. The variation in the intensity of optical absorption with the ionic radius of the alkaline earth ion has been explained based on the Coulombic forces. By correlating the EPR and optical absorption spectral data, the nature of the in-plane {sigma} bonding between Cu{sup 2+} ion and the ligands is estimated. From the fundamental ultraviolet absorption edges of the glasses, the optical energy gap (E {sub opt}) and the Urbach energy ({delta}E) are evaluated. The variation in E {sub opt} and {delta}E is explained based on the number of defect centers in the glass.

  7. Structural, electronic and mechanical properties of alkaline earth metal oxides MO (M=Be, Mg, Ca, Sr, Ba)

    NASA Astrophysics Data System (ADS)

    Cinthia, A. Jemmy; Priyanga, G. Sudha; Rajeswarapalanichamy, R.; Iyakutti, K.

    2015-04-01

    The structural, electronic and mechanical properties of alkaline earth metal oxides MO (M=Be, Mg, Ca, Sr, Ba) in the cubic (B1, B2 and B3) phases and in the wurtzite (B4) phase are investigated using density functional theory calculations as implemented in VASP code. The lattice constants, cohesive energy, bulk modulus, band structures and the density of states are computed. The calculated lattice parameters are in good agreement with the experimental and the other available theoretical results. Electronic structure reveals that all the five alkaline earth metal oxides exhibit semiconducting behavior at zero pressure. The estimated band gaps for the stable wurtzite phase of BeO is 7.2 eV and for the stable cubic NaCl phases of MgO, CaO, SrO and BaO are 4.436 eV, 4.166 eV, 4.013 eV, and 2.274 eV respectively. A pressure induced structural phase transition occurs from wurtzite (B4) to NaCl (B1) phase in BeO at 112.1 GPa and from NaCl (B1) to CsCl (B2) phase in MgO at 514.9 GPa, in CaO at 61.3 GPa, in SrO at 42 GPa and in BaO at 14.5 GPa. The elastic constants are computed at zero and elevated pressures for the B4 and B1 phases for BeO and for the B1 and B2 phases in the case of the other oxides in order to investigate their mechanical stability, anisotropy and hardness. The sound velocities and the Debye temperatures are calculated for all the oxides using the computed elastic constants.

  8. Design of ternary alkaline-earth metal Sn(II) oxides with potential good p-type conductivity

    SciTech Connect

    Du, Mao -Hua; Singh, David J.; Zhang, Lijun; Li, Yuwei; Xu, Qiaoling; Ma, Yanming; Zheng, Weitao

    2016-04-19

    Oxides with good p-type conductivity have been long sought after to achieve high performance all-oxide optoelectronic devices. Divalent Sn(II) based oxides are promising candidates because of their rather dispersive upper valence bands caused by the Sn-5s/O-2p anti-bonding hybridization. There are so far few known Sn(II) oxides being p-type conductive suitable for device applications. Here, we present via first-principles global optimization structure searches a material design study for a hitherto unexplored Sn(II)-based system, ternary alkaline-earth metal Sn(II) oxides in the stoichiometry of MSn2O3 (M = Mg, Ca, Sr, Ba). We identify two stable compounds of SrSn2O3 and BaSn2O3, which can be stabilized by Sn-rich conditions in phase stability diagrams. Their structures follow the Zintl behaviour and consist of basic structural motifs of SnO3 tetrahedra. Unexpectedly they show distinct electronic properties with band gaps ranging from 1.90 (BaSn2O3) to 3.15 (SrSn2O3) eV, and hole effective masses ranging from 0.87 (BaSn2O3) to above 6.0 (SrSn2O3) m0. Further exploration of metastable phases indicates a wide tunability of electronic properties controlled by the details of the bonding between the basic structural motifs. Lastly, this suggests further exploration of alkaline-earth metal Sn(II) oxides for potential applications requiring good p-type conductivity such as transparent conductors and photovoltaic absorbers.

  9. Sign Changes in the Electric Dipole Moment of Excited States in Rubidium-Alkaline Earth Diatomic Molecules

    NASA Astrophysics Data System (ADS)

    Pototschnig, Johann V.; Lackner, Florian; Hauser, Andreas W.; Ernst, Wolfgang E.

    2015-06-01

    In a recent series of combined experimental and theoretical studies we investigated the ground state and several excited states of the Rb-alkaline earth molecules RbSr and RbCa. The group of alkali-alkaline earth (AK-AKE) molecules has drawn attention for applications in ultracold molecular physics and the measurement of fundamental constants due to their large permanent electric and magnetic dipole moments in the ground state. These properties should allow for an easy manipulation of the molecules and simulations of spin models in optical lattices. In our studies we found that the permanent electric dipole moment points in different directions for certain electronically excited states, and changes the sign in some cases as a function of bond length. We summarize our results, give possible causes for the measured trends in terms of molecular orbital theory and extrapolate the tendencies to other combinations of AK and AKE - elements. F. Lackner, G. Krois, T. Buchsteiner, J. V. Pototschnig, and W. E. Ernst, Phys. Rev. Lett., 2014, 113, 153001; G. Krois, F. Lackner, J. V. Pototschnig, T. Buchsteiner, and W. E. Ernst, Phys. Chem. Chem. Phys., 2014, 16, 22373; J. V. Pototschnig, G. Krois, F. Lackner, and W. E. Ernst, J. Chem. Phys., 2014, 141, 234309 J. V. Pototschnig, G. Krois, F. Lackner, and W. E. Ernst, J. Mol. Spectrosc., in Press (2015), doi:10.1016/j.jms.2015.01.006 M. Kajita, G. Gopakumar, M. Abe, and M. Hada, J. Mol. Spectrosc., 2014, 300, 99-107 A. Micheli, G. K. Brennen, and P. Zoller, Nature Physics, 2006, 2, 341-347

  10. Design of ternary alkaline-earth metal Sn(II) oxides with potential good p-type conductivity

    DOE PAGES

    Du, Mao -Hua; Singh, David J.; Zhang, Lijun; ...

    2016-04-19

    Oxides with good p-type conductivity have been long sought after to achieve high performance all-oxide optoelectronic devices. Divalent Sn(II) based oxides are promising candidates because of their rather dispersive upper valence bands caused by the Sn-5s/O-2p anti-bonding hybridization. There are so far few known Sn(II) oxides being p-type conductive suitable for device applications. Here, we present via first-principles global optimization structure searches a material design study for a hitherto unexplored Sn(II)-based system, ternary alkaline-earth metal Sn(II) oxides in the stoichiometry of MSn2O3 (M = Mg, Ca, Sr, Ba). We identify two stable compounds of SrSn2O3 and BaSn2O3, which can bemore » stabilized by Sn-rich conditions in phase stability diagrams. Their structures follow the Zintl behaviour and consist of basic structural motifs of SnO3 tetrahedra. Unexpectedly they show distinct electronic properties with band gaps ranging from 1.90 (BaSn2O3) to 3.15 (SrSn2O3) eV, and hole effective masses ranging from 0.87 (BaSn2O3) to above 6.0 (SrSn2O3) m0. Further exploration of metastable phases indicates a wide tunability of electronic properties controlled by the details of the bonding between the basic structural motifs. Lastly, this suggests further exploration of alkaline-earth metal Sn(II) oxides for potential applications requiring good p-type conductivity such as transparent conductors and photovoltaic absorbers.« less

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

    PubMed

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

    2014-07-01

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

  12. Theoretical Studies of the Spin Hamiltonian Parameters and Local Distortions for Cu2+ in Alkaline Earth Lead Zinc Phosphate Glasses

    NASA Astrophysics Data System (ADS)

    Wang, Bo-Kun; Wu, Shao-Yi; Yuan, Zi-Yi; Liu, Zi-Xuan; Jiang, Shi-Xin; Liu, Zheng; Yao, Zi-Jian; Teng, Bao-Hua; Wu, Ming-He

    2016-08-01

    The spin Hamiltonian parameters and local structures are theoretically studied for Cu2+-doped alkaline earth lead zinc phosphate (RPPZ, R=Mg, Ca, Sr, and Ba) glasses based on the high-order perturbation calculations for a tetragonally elongated octahedral 3d9 cluster. The relative elongation ratios are found to be ρ≈3.2%, 4.4%, 4.6%, and 3.3% for R=Mg, Ca, Sr, and Ba, respectively, because of the Jahn-Teller effect. The whole decreasing crystal-field strength Dq and orbital reduction factor k from Mg to Sr are ascribed to the weakening electrostatic coulombic interactions and the increasing probability of productivity of nonbridge oxygen (and hence increasing Cu2+-O2- electron cloud admixtures) under PbO addition, respectively, with increasing alkali earth ionic radius. The anomalies (the largest Dq and the next highest k among the systems) for R=Ba are attributed to the cross linkage of this large cation in the network. The overall increasing order (Mg≤Ba

  13. Structural diversity in binuclear complexes of alkaline earth metal ions with 4,6-diacetylresorcinol

    NASA Astrophysics Data System (ADS)

    Shebl, Magdy; Khalil, Saied M. E.; Taha, A.; Mahdi, M. A. N.

    2012-11-01

    A new series of binuclear and mixed-ligand complexes with the general formula: [M 2(LO)yClz]; where M = Mg(II), Ca(II), Sr(II) and Ba(II); H2L = 4,6-diacetylresorcinol, the secondary ligand L' = acetylacetone (acac), 8-hydroxyquinoline (8-HQ) or 2,2'-bipyridyl (Bipy), n = 0-2, m = 1, 2, x = 0, 1, 2, 4, y = 0, 2, 4, 5 and z = 0-2; have been synthesized. They have been characterized by the analytical and spectral methods (IR, 1H NMR and mass) as well as TGA and molar conductivity measurements. The spectroscopic and conductance data suggested that the H2L ligand behaves as a neutral, monobasic or dibasic tetradentate ligand, depending on the basicity of the secondary ligand, through the two phenolic and two carbonyl groups. Binuclear octahedral geometry has been assigned to all of the prepared complexes in various molar ratios 2:2; 2:2:2; 1:2:1 and 1:2:4 (L:M:L'). Molecular orbital calculations were performed for the ligands and their complexes using Hyperchem 7.52 program on the bases of PM3 level and the results were correlated with the experimental data. The ligand and some of its alkaline metal(II) complexes showed antibacterial activity towards some of Gram-positive and Gram-negative bacteria, yeast (Candida albicans) and fungus (Aspergillus fumigatus).

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

    NASA Astrophysics Data System (ADS)

    Patki, Gauri Dilip

    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.

  15. Recent progress on earth abundant hydrogen evolution reaction and oxygen evolution reaction bifunctional electrocatalyst for overall water splitting in alkaline media

    NASA Astrophysics Data System (ADS)

    Jamesh, Mohammed Ibrahim

    2016-11-01

    Electrochemical water-splitting is one of the promising ways for producing clean chemical fuel (Hydrogen) while cheap-earth-abundant-bifunctional-electrocatalyst is one of the possible way for improving the overall cost efficiency of water-splitting. This paper reviews the chemical state, hydrogen and oxygen evolution reaction activity in alkaline media, overall water-splitting performance in alkaline media, stability, and possible-factors for improving its efficiency of various kinds of recently reported electrocatalyst such as Ni-P, Co-P, Ni-Co-P, graphene-Co-P, O/N/C-Co/Ni, Ni-S, B-Ni/Co, Ni-Co, Mo, Se, Fe, Mn/Zn/Ti, and metal-free based earth-abundant-bifunctional-electrocatalyst. This paper also reviews and highlights the remarkable water splitting performance of the earth-abundant-bifunctional-electrocatalyst those exhibit better or well comparable with Pt/C//RuO2.

  16. A dehydrogenation mechanism of metal hydrides based on interactions between Hdelta+ and H-.

    PubMed

    Lu, Jun; Fang, Zhigang Zak; Sohn, Hong Yong

    2006-10-16

    This paper describes a reaction mechanism that explains the dehydrogenation reactions of alkali and alkaline-earth metal hydrides. These light metal hydrides, e.g., lithium-based compounds such as LiH, LiAlH4, and LiNH2, are the focus of intense research recently as the most promising candidate materials for on-board hydrogen storage applications. Although several interesting and promising reactions and materials have been reported, most of these reported reactions and materials have been discovered by empirical means because of a general lack of understanding of any underlying principles. This paper describes an understanding of the dehydrogenation reactions on the basis of the interaction between negatively charged hydrogen (H-, electron donor) and positively charged hydrogen (Hdelta+, electron acceptor) and experimental evidence that captures and explains many observations that have been reported to date. This reaction mechanism can be used as a guidance for screening new material systems for hydrogen storage.

  17. Halogen-abstraction reactions from chloromethane and bromomethane molecules by alkaline-earth monocations.

    PubMed

    Redondo, Pilar; Largo, Antonio; Rayón, Víctor Manuel; Molpeceres, Germán; Sordo, José Ángel; Barrientos, Carmen

    2014-08-14

    The reactions, in the gas phase, between alkali-earth monocations (Mg(+), Ca(+), Sr(+), Ba(+)) and CH3X (X = Cl, Br) have been theoretically studied. The stationary points on the potential energy surfaces were characterized at the Density Functional Theory level on the framework of the mPW1K functional with the QZVPP Ahlrichs's basis sets. A complementary kinetics study has also been performed using conventional/variational microcanonical transition state theory. In the reactions of Mg(+) with either chloro- or bromomethane the transition structure lies in energy clearly above the reactants rendering thermal activation of CH3Cl or CH3Br extremely improbable. The remaining reactions are exothermic and barrierless processes; thus carbon-halogen bonds in chloro- or bromomethane can be activated by calcium, strontium or barium monocations to obtain the metal halogen cation and the methyl radical. The Mulliken population analysis for the stationary points of the potential energy surfaces supports a "harpoon"-like mechanism for the halogen-atom abstraction processes. An analysis of the bonding situation for the stationary points on the potential energy surface has also been performed in the framework of the quantum theory of atoms in molecules.

  18. A new N-hydroxyethyliminodiacetic acid modified core-shell silica phase for chelation ion chromatography of alkaline earth, transition and rare earth elements.

    PubMed

    McGillicuddy, Nicola; Nesterenko, Ekaterina P; Nesterenko, Pavel N; Stack, Elaine M; Omamogho, Jesse O; Glennon, Jeremy D; Paull, Brett

    2013-12-20

    Bare core-shell silica (1.7μm) has been modified with iminodiacetic acid functional groups via standard silane chemistry, forming a new N-hydroxyethyliminodiacetic acid (HEIDA) functionalised core-shell stationary phase. The column was applied in high-performance chelation ion chromatography and evaluated for the retention of alkaline earth, transition and heavy metal cations. The influence of nitric acid eluent concentration, addition of complexing agent dipicolinic acid, eluent pH and column temperature on the column performance was investigated. The efficiencies obtained for transition and heavy metal cations (and resultant separations) were comparable or better than those previously obtained for alternative fully porous silica based chelation stationary phases, and a similarly modified monolithic silica column, ranging from ∼15 to 56μm HETP. Increasing the ionic strength of the eluent with the addition of KNO3 (0.75M) and increasing the column temperature (70°C) facilitated the isocratic separation of a mixture of 14 lanthanides and yttrium in under 12min, with HETP averaging 18μm (7μm for Ce(III)).

  19. Structures and stabilities of alkaline earth metal peroxides XO2 (X=Ca, Be, Mg) studied by a genetic algorithm

    SciTech Connect

    Zhao, Xin; Nguyen, Manh Cuong; Wang, Cai-Zhuang; Ho, Kai-Ming

    2013-09-17

    The structures and stabilities of alkaline earth metal peroxides XO2 (X = Ca, Be, Mg) were studied using an adaptive genetic algorithm (GA) for global structure optimization in combination with first-principles calculations. From the adaptive GA search, we obtained an orthorhombic structure for CaO2 with 12 atoms in the unit cell, which is energetically more favorable than the previously proposed structures. Reaction energy of the decomposition CaO2 → CaO + 1/2O2 determined by density functional theory (DFT) calculation shows that this orthorhombic calcium peroxide structure is thermodynamically stable. The simulated X-ray diffraction (XRD) pattern using our predicted structure is in excellent agreement with experimental data. We also show that crystal phase BeO2 is unlikely to exist under normal conditions. MgO2 has a cubic pyrite structure, but it is not stable against decomposition: MgO2 → MgO + 1/2O2.

  20. X-ray Diffraction Studies of the Structure and Thermochemistry of Alkaline-Earth Oxide-Coated Thermionic Cathodes

    NASA Technical Reports Server (NTRS)

    Karikari, E. K.; Bassey, E.; Wintucky, Edwin G.

    1998-01-01

    NASA LeRC has a broad, active cathode technology development program in which both experimental and theoretical studies are being employed to further development of thermionic cathodes for use as electron sources in vacuum devices for communications and other space applications. One important type of thermionic cathode under development is the alkaline-earth oxide-coated (BaO, SrO, CaO) cathode. Significant improvements in the emission characteristics of this cathode have been obtained through modification of the chemical composition and morphology of the oxide coating, with the best result thus far coming from the addition of In2O3 and Sc2O3. Whereas the In2O3 produces a finer, more uniform particle structure, the exact chemical state and role of the Sc2O3 in the emission enhancement is unknown. The purpose of this cooperative agreement is to combine the studies of the surface chemistry and electron emission at NASA LeRC of chemically modified oxide coatings with a study of the thermochemistry and crystal structure using X-ray diffraction equipment and expertise at Clark Atlanta University (CAU). The study at CAU is intended to provide the description and understanding of the structure and thermochemistry needed for further improvement and optimization of the modified coatings. A description of the experimental procedure, preliminary X-ray diffraction test results, together with the design of an ultrahigh vacuum chamber necessary for high temperature thermochemistry studies will be presented.

  1. Selective oxidation of methanol to hydrogen over gold catalysts promoted by alkaline-earth-metal and lanthanum oxides.

    PubMed

    Hereijgers, Bart P C; Weckhuysen, Bert M

    2009-01-01

    A series of alumina-supported gold catalysts was investigated for the CO-free production of hydrogen by partial oxidation of methanol. The addition of alkaline-earth metal oxide promoters resulted in a significant improvement of the catalytic performance. The methanol conversion was ca. 85 % with all studied catalyst materials, however, the selectivity for hydrogen increased from 15 % to 51 % when going from the unpromoted to a BaO-promoted catalyst. The formation of the undesired byproducts CO, methane, and dimethyl ether was considerably reduced as well. The observed trend in catalyst performance follows the trend in increasing basicity of the studied promoter elements, indicating a chemical effect of the promoter material. Superior catalytic performance, in terms of H(2) and CO selectivity, was obtained with a Au/La(2)O(3) catalyst. At 300 degrees C the hydrogen selectivity reached 80 % with only 2 % CO formation, and the catalyst displayed a stable performance over at least 24 h on-stream. Furthermore, the formation of CO was found to be independent of the oxygen concentration in the feed. The commercial lanthanum oxide used in this study had a low specific surface area, which led to the formation of relative large gold particles. Therefore, the catalytic activity could be enhanced by decreasing the gold particle size through deposition on lanthanum oxide supported on high-surface-area alumina.

  2. Synergetic effect of alkaline earth metal oxides and iron oxides on the degradation of hexachlorobenzene and its degradation pathway.

    PubMed

    Su, Guijin; Liu, Yexuan; Huang, Linyan; Shi, Yali; Zhang, Aiqian; Zhang, Lixia; Liu, Wenbin; Gao, Lirong; Zheng, Minghui

    2013-01-01

    The degradation of hexachlorobenzene (HCB) was carried out over physical mixtures of a series of alkaline earth metal oxides (MO: M=Mg, Ca, Sr, Ba) and iron oxides with different crystal types (Fe(x)O(y):Fe(2)O(3) or Fe(3)O(4)) at 300°C. These physical mixtures all showed a synergetic effect toward the degradation of HCB. A range of degradation products were identified by various methods, including tri- to penta-chlorobenzenes by gas chromatography/mass spectrometry (GC-MS), tri- to penta-chlorophenols, tetrachlorocatechol (TCC) and tetrachlorohydroquinone (TCHQ) by GC-MS after derivatization, and formic and acetic acids by ion chromatography. Two degradation pathways, hydrodechlorination and oxidative degradation, appear to occur competitively. However, more sequential chlorinated benzene and phenol congeners were formed over mixed MO/Fe(3)O(4) than over mixed MO/Fe(2)O(3) under the same conditions. The oxidative reaction dominated over mixed MO/Fe(2)O(3) and was promoted as the major reaction by the synergetic effect, while both the oxidative and hydrodechlorination reactions were important over mixed MO/Fe(3)O(4), and both pathways are remarkably promoted by the synergetic effect. The enhanced hydrodechlorination may be attributed to free electrons generated by the transformation of Fe(3)O(4) into Fe(2)O(3), and hydrogen provided by water adsorbed on the MO.

  3. Cardiac ryanodine receptor: Selectivity for alkaline earth metal cations points to the EF-hand nature of luminal binding sites.

    PubMed

    Gaburjakova, Jana; Gaburjakova, Marta

    2016-06-01

    A growing body of evidence suggests that the regulation of cardiac ryanodine receptor (RYR2) by luminal Ca(2+) is mediated by luminal binding sites located on the RYR2 channel itself and/or its auxiliary protein, calsequestrin. The localization and structure of RYR2-resident binding sites are not known because of the lack of a high-resolution structure of RYR2 luminal regions. To obtain the first structural insight, we probed the RYR2 luminal face stripped of calsequestrin by alkaline earth metal divalents (M(2+): Mg(2+), Ca(2+), Sr(2+) or Ba(2+)). We show that the RYR2 response to caffeine at the single-channel level is significantly modified by the nature of luminal M(2+). Moreover, we performed competition experiments by varying the concentration of luminal M(2+) (Mg(2+), Sr(2+) or Ba(2+)) from 8 mM to 53 mM and investigated its ability to compete with 1mM luminal Ca(2+). We demonstrate that all tested M(2+) bind to exactly the same RYR2 luminal binding sites. Their affinities decrease in the order: Ca(2+)>Sr(2+)>Mg(2+)~Ba(2+), showing a strong correlation with the M(2+) affinity of the EF-hand motif. This indicates that the RYR2 luminal binding regions and the EF-hand motif likely share some structural similarities because the structure ties directly to the function.

  4. Dissolution of glass wool, rock wool and alkaline earth silicate wool: morphological and chemical changes in fibers.

    PubMed

    Campopiano, Antonella; Cannizzaro, Annapaola; Angelosanto, Federica; Astolfi, Maria Luisa; Ramires, Deborah; Olori, Angelo; Canepari, Silvia; Iavicoli, Sergio

    2014-10-01

    The behavior of alkaline earth silicate (AES) wool and of other biosoluble wools in saline solution simulating physiological fluids was compared with that of a traditional wool belonging to synthetic vitreous fibers. Morphological and size changes of fibers were studied by scanning electron microscopy (SEM). The elements extracted from fibers were analyzed by inductively coupled plasma atomic emission spectrometry. SEM analysis showed a larger reduction of length-weighted geometric mean fiber diameter at 4.5 pH than at 7.4 pH. At the 7.4 pH, AES wool showed a higher dissolution rate and a dissolution time less than a few days. Their dissolution was highly non-congruent with rapid leaching of calcium. Unlike rock wool, glass wool dissolved more rapidly at physiological pH than at acid pH. Dissolution of AES and biosoluble rock wool is accompanied by a noticeable change in morphology while by no change for glass wool. Biosoluble rock wool developed a leached surface with porous honeycomb structure. SEM analysis showed the dissolution for glass wool is mainly due to breakage transverse of fiber at pH 7.4. AES dissolution constant (Kdis) was the highest at pH 7.4, while at pH 4.5 only biosoluble rockwool 1 showed a higher Kdis.

  5. First-Principles Calculation of Solution Energy of Alkaline-Earth Metal Elements to BaTiO3

    NASA Astrophysics Data System (ADS)

    Moriwake, Hiroki; Hirayama, Tsukasa; Ikuhara, Yuichi; Tanaka, Isao

    2007-10-01

    Quantitative analysis of the solution energy of alkaline-earth metal elements to perovskite-type BaTiO3 was carried out by a first-principles calculation combined with thermodynamics theory. The solution energies of neutral solute and a compensated solute with an oxygen vacancy were systematically calculated. They were obtained for two cation sites and four thermodynamical conditions with different chemical potentials of constituent atoms. Both Ca and Sr preferably occupy the Ba site of BaTiO3. On the other hand, Mg occupies the Ti site. This corresponds well to the widely accepted experimental findings regarding site preference. Moreover, under the condition of coexising BaO, CaO and BaTiO3, energy difference between the Ba-site solution and O-vacancy compensated Ti-site solution of Ca ions has been found to be smaller than that of Sr. Under this condition, the O-vacancy compensated Ti-site solution of Ca should be favorable compared with that of Sr. The same number of oxygen vacancies as Ca ions occupying Ti sites can be introduced. This also explains well experimental feature of the Ca-doped BaTiO3-based nonreducible multilayer ceramics capacitor (MLCC) materials regarding solution site of the Ca ion and abundance of O-vacancy.

  6. CO2 gasification reactivity of biomass char: catalytic influence of alkali, alkaline earth and transition metal salts.

    PubMed

    Lahijani, Pooya; Zainal, Zainal Alimuddin; Mohamed, Abdul Rahman; Mohammadi, Maedeh

    2013-09-01

    This study investigates the influence of alkali (Na, K), alkaline earth (Ca, Mg) and transition (Fe) metal nitrates on CO2 gasification reactivity of pistachio nut shell (PNS) char. The preliminary gasification experiments were performed in thermogravimetric analyzer (TGA) and the results showed considerable improvement in carbon conversion; Na-char>Ca-char>Fe-char>K-char>Mg-char>raw char. Based on TGA studies, NaNO3 (with loadings of 3-7 wt%) was selected as the superior catalyst for further gasification studies in bench-scale reactor; the highest reactivity was devoted to 5 wt% Na loaded char. The data acquired for gasification rate of catalyzed char were fitted with several kinetic models, among which, random pore model was adopted as the best model. Based on obtained gasification rate constant and using the Arrhenius plot, activation energy of 5 wt% Na loaded char was calculated as 151.46 kJ/mol which was 53 kJ/mol lower than that of un-catalyzed char.

  7. A Density Functional Theory Study of Codoping Characteristics of Sulfur with Alkaline Earth in Delafossite CuAlO2

    NASA Astrophysics Data System (ADS)

    Liu, Qi-Jun; Qin, Han; Liu, Zheng-Tang

    2016-04-01

    The structural, electronic properties and formation energies of sulfur and alkaline earth codoped delafossite CuAlO2 have been investigated using the first-principles density functional theory calculations. Our results reveal that the volume of codoping systems increases with the increasing atomic radius of metal atoms. The formation energies under different growth conditions have been calculated, showing that the codoping systems are formed easily under O-rich growth conditions. Electronic band structures and density of states have been obtained. The decreased bandgaps, enhanced covalence and appearance of electron acceptors after codoping are all good for p-type conductivity. Supported by the National Natural Science Foundation of China under Grant Nos. 11347199, 51402244, and 11547311, the Specialized Research Fund for Doctoral Program of Higher Education of China under Grant No. 20130184120028, the Fundamental Research Fund for the Central Universities, China under Grant Nos. 2682014CX084, 2682014ZT30, and 2682014ZT31, and the fund of the State Key Laboratory of Solidification Processing in NWPU under Grant No. SKLSP201511

  8. Hydride compressor

    DOEpatents

    Powell, James R.; Salzano, Francis J.

    1978-01-01

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

  9. Amido-based potassium-alkaline earth metallates--synthesis and structures of heterobimetallic complexes of heavy s-block elements.

    PubMed

    Glock, Carsten; Görls, Helmar; Westerhausen, Matthias

    2011-08-28

    The metathesis reaction of potassium N-isopropylanilide with alkaline earth metal diiodides of calcium, strontium and barium in a molar ratio of 4:1 yields the corresponding alkaline earth metalates of the type [(THF)(n)K(μ-NPhiPr)(2)Ae(μ-NPhiPr)(2)K(THF)(n)] (1: Ae = Ca, n = 2). Stabilization and crystallization of such derivatives succeeds after exchange of the THF ligands by multidentate amino bases such as tetramethylethylenediamine (TMEDA) or pentamethyldiethylenetriamine (PMDETA). The influence of the size and hardness of the alkaline earth metal center on the molecular structures is studied with [(L)K(μ-NPhiPr)(2)Ae(μ-NPhiPr)(2)K(L)] (2: Ae = Ca, L = TMEDA; 3: Ae = Sr, L = TMEDA; 4: Ae = Sr, L = PMDETA; and 5: Ae = Ba, L = PMDETA). The molecular structures are dominated by (attractive and repulsive) electrostatic and steric factors leading to a shortening of the non-bonding AeK distances from calcium to barium.

  10. Monitoring of photoluminescence decay by alkali and alkaline earth metal cations using a photoluminescent bolaamphiphile self-assembly as an optical probe.

    PubMed

    Kim, Sunhyung; Kwak, Jinyoung; Lee, Sang-Yup

    2014-05-01

    Photoluminescence (PL) decay induced by the displacement of an ionic fluorescence component, Tb(3+), with alkali and alkaline earth metal cations was investigated using photoluminescent spherical self-assemblies as optical probes. The photoluminescent spherical self-assembly was prepared by the self-organization of a tyrosine-containing bolaamphiphile molecule with a photosensitizer and Tb(3+) ion. The lanthanide ion, Tb(3+), electrically bound to the carboxyl group of the bolaamphiphile molecule, was displaced by alkali and alkaline earth metal cations that had stronger electrophilicity. The PL of the self-assembly decayed remarkably due to the substitution of lanthanide ions with alkali and alkaline earth metal cations. The PL decay showed a positive correlation with cation concentration and was sensitive to the cation valency. Generally, the PL decay was enhanced by the electrophilicity of the cations. However, Ca(2+) showed greater PL decay than Mg(2+) because Ca(2+) could create various complexes with the carboxyl groups of the bolaamphiphile molecule. Microscopic and spectroscopic investigations were conducted to study the photon energy transfer and displacement of Tb(3+) by the cation exchange. This study demonstrated that the PL decay by the displacement of the ionic fluorescent compound was applied to the detection of various cations in aqueous media and is applicable to the development of future optical sensors.

  11. Multidimensional (0D to 3D) Alkaline-Earth Metal Diphosphonates: Synthesis, Structural Diversity, and Luminescence Properties.

    PubMed

    Senthil Raja, Duraisamy; Lin, Pin-Chun; Liu, Wei-Ren; Zhan, Jun-Xiang; Fu, Xin-Yi; Lin, Chia-Her

    2015-05-04

    A series of new alkaline-earth metal diphosphonate frameworks were successfully synthesized under solvothermal reaction condition (160 °C, 3 d) using 1-hydroxyethylidene-1,1-diphosphonic acid (CH3C(OH)(H2PO3)2, hedpH4) as a diphosphonate building block and Mg(II), Ca(II), Sr(II), or Ba(II) ions as alkaline-earth metal ion centers in water, dimethylformamide, and/or EtOH media. These diphosphonate frameworks, (H2NMe2)4[Mg(hedpH2)3]·3H2O (1), (H2NMe2)2[Ca(hedpH2)2] (2), (H2NMe2)2[Sr3(hedpH2)4(H2O)2] (3), and [Ba3(hedpH2)3]·H2O (4) exhibited interesting structural topologies (zero-, one-, two-, and three-dimensional (0D, 1D, 2D, and 3D, respectively)), which are mainly depending on the metal ions and the solvents used in the synthesis. The single-crystal analysis of these newly synthesized compounds revealed that 1 was a 0D molecule, 2 has 1D chains, 3 was a 3D molecule, and 4 has 2D layers. All compounds were further characterized using thermogravimetric analysis, solid-state (31)P NMR, powder X-ray diffraction analysis, UV-vis spectra, and infrared spectroscopy. In addition, Eu(III)- and Tb(III)-doped compounds of 1-4, namely, (H2NMe2)4[Ln(x)Mg(1-x)(hedpH2)2(hedpH(2-x))]·3H2O (1Ln), (H2NMe2)2[Ln(x)Ca(1-x)(hedpH2)(hedpH(2-x))] (2Ln), (H2NMe2)2[Ln(x)Sr(3-x)(hedpH2)3(hedpH(2-x))(H2O)2] (3Ln), and [Ln(x)Ba(3-x)(hedpH2)2(hedpH(2-x))]·H2O (4Ln) (where Ln = Eu, Tb), were synthesized, and their photoluminescence properties were studied. The quantum yield of 1Eu-4Eu was measured with reference to commercial red phosphor, Y2O2S:Eu(3+) (YE), and the quantum yield of terbium-doped compounds 1Tb-4Tb was measured with reference to commercial green-emitting phosphor CeMgAl10O17:Tb(3+). Interestingly, the compound 2Eu showed very high quantum yield of 92.2%, which is better than that of the reference commercial red phosphor, YE (90.8%).

  12. Separation of alkali, alkaline earth and rare earth cations by liquid membranes containing macrocyclic carriers. Third progress report, September 1, 1980-April 1, 1981

    SciTech Connect

    Christensen, J.J.

    1981-04-15

    The overall objective of this project is to study the use of liquid membrane systems employing macrocyclic ligand carriers in making separations among metal cations. During the third year of the project, work continued in the development of a mathematical model to describe cation transport. The model was originally developed to describe the relationship between cation transport rate (J/sub M/) and the cation-macrocycle stability constant (K). The model was tested by determining the rates of transport of alkali and alkaline earth cations through chloroform membranes containing carrier ligands where the stability constants for their reaction with cations in methanol were known. From the results, it is clear that the model correctly describes the dependence of J/sub M/ on log K. The model also correctly describes the effect of cation concentration and carrier concentration on cation transport rates, as detailed in the previous progress report. During the third year of the project, the transport model was expanded so as to apply to competitive transport of cations from mixtures of two cations in the source aqueous phase. Data were collected under these conditions and the ability of the model to predict the flux of each cation was tested. Representative data of this type are presented along with corresponding data which were obtained when each cation was transported by the same carrier from a source phase containing only that cation. Comparison of transport rates determined under the two experimental conditions indicates that the relationship between the two sets of data is complex. To date, a few of these data involving transport from binary cation mixtures have been tested against the transport model. It was found that the model correctly predicts the cation fluxes from cation mixtures. These preliminary results indicate that the transport model can successfully predict separation factors when cation mixtures are used.

  13. Discrete divalent rare-earth cationic ROP catalysts: ligand-dependent redox behavior and discrepancies with alkaline-earth analogues in a ligand-assisted activated monomer mechanism.

    PubMed

    Liu, Bo; Roisnel, Thierry; Maron, Laurent; Carpentier, Jean-François; Sarazin, Yann

    2013-03-18

    The first solvent-free cationic complexes of the divalent rare-earth metals, [{RO}RE(II) ](+) [A](-) (RE(II) =Yb(II) , 1; Eu(II) , 2) and [{LO}RE(II) ](+) [A](-) ([A](-) =[H2 N{B(C6 F5 )3 }2 ](-) ; RE(II) =Yb(II) , 3; Eu(II) , 4), have been prepared by using highly chelating monoanionic aminoether-fluoroalkoxide ({RO}(-) ) and aminoether-phenolate ({LO}(-) ) ligands. Complexes 1 and 2 are structurally related to their alkaline-earth analogues [{RO}AE](+) [A](-) (AE=Ca, 5; Sr, 6). Yet, the two families behave very differently during catalysis of the ring-opening polymerization (ROP) of L-lactide (L-LA) and trimethylene carbonate (TMC) performed under immortal conditions with excess BnOH as an exogenous chain-transfer agent. The ligand was found to strongly influence the behavior of the RE(II) complexes during ROP catalysis. The fluoroalkoxide RE(II) catalysts 1 and 2 are not oxidized under ROP conditions, and compare very favorably with their Ca and Sr congeners 5 and 6 in terms of activity (turnover frequency (TOF) in the range 200-400 molL-LA (molEu  h(-1) )) and control over the parameters during the immortal ROP of L-LA (Mn,theor ≈Mn,SEC , Mw /Mn <1.05). The Eu(II) -phenolate 4 provided one of the most effective ROP cationic systems known to date for L-LA polymerization, exhibiting high activity (TOF up to 1 880 molL-LA ⋅(molEu  h)(-1) ) and good control (Mw /Mn =1.05). By contrast, upon addition of L-LA the Yb(II) -phenolate 3 immediately oxidizes to inactive RE(III) species. Yet, the cyclic carbonate TMC was rapidly polymerized by combinations of 3 (or even 1) and BnOH, revealing excellent activities (TOF=5000-7000 molTMC ⋅(molEu  h)(-1) ) and unusually high control (Mn,theor ≈Mn,SEC , Mw /Mn <1.09); under identical conditions, the calcium derivative 5 was entirely inert toward TMC. Based on experimental and kinetic data, a new ligand-assisted activated monomer ROP mechanism is suggested, in which the so-called ancillary ligand plays a

  14. DEVELOPMENT OF GLASS COMPOSITIONS TO IMMOBILIZE ALKALI, ALKALINE EARTH, LANTHANIDE AND TRANSITION METAL FISSION PRODUCTS FROM NUCLEAR FUEL REPROCESSING

    SciTech Connect

    Marra, J.; Billings, A.

    2009-06-24

    The Advanced Fuel Cycle Initiative (AFCI) waste management strategy revolves around specific treatment of individual or groups of separated waste streams. A goal for the separations processes is to efficiently manage the waste to be dispositioned as high level radioactive waste. The Advanced Fuel Cycle Initiative (AFCI) baseline technology for immobilization of the lanthanide (Ln) and transition metal fission product (TM) wastes is vitrification into a borosilicate glass. A current interest is to evaluate the feasibility of vitrifying combined waste streams to most cost effectively immobilize the wastes resulting from aqueous fuel reprocessing. Studies showed that high waste loadings are achievable for the Ln only (Option 1) stream. Waste loadings in excess of 60 wt % (on a calcined oxide basis) were demonstrated via a lanthanide borosilicate (LaBS) glass. The resulting glasses had excellent relative durability as determined by the Product Consistency Test (PCT). For a combined Ln and TM waste stream glass (Option 2), noble metal solubility was found to limit waste loading. However, the measured PCT normalized elemental releases for this glass were at least an order of magnitude below that of Environmental Assessment (EA) glass. Current efforts to evaluate the feasibility of vitrifying combined Ln, TM, alkali (Cs is the primary radionuclide of concern) and alkaline earth (Sr is the primary radionuclide of concern) wastes (Option 3) have shown that these approaches are feasible. However, waste loading limitations with respect to heat load (Cs/Sr loading), molybdenum solubility and/or noble metal solubility will likely be realized and must be considered in determining the cost effectiveness of these approaches.

  15. Honeycomb-shaped coordination polymers based on the self-assembly of long flexible ligands and alkaline-earth ions

    SciTech Connect

    Lian, Chen; Liu, Liu; Guo, Xu; Long, Yinshuang; Jia, Shanshan; Li, Huanhuan; Yang, Lirong

    2016-01-15

    Two novel coordination polymers, namely, [Ca(NCP){sub 2}]{sub ∞} (I) and [Sr(NCP){sub 2}]{sub ∞} (II) were synthesized under hydrothermal conditions based on 2-(4-carboxyphenyl)imidazo(4,5-f)-(1,10)phenanthroline (HNCP) and characterized by elemental analysis, infrared spectrometry, X-ray powder diffraction and single crystal X-ray diffraction. Findings indicate that I and II are isomorphous and isostructural, containing the unit of M(NCP{sup −}){sub 4} (M=Ca(II) and Sr(II)), based on which to assemble into three-dimensional (3D) porous 4-fold interpenetration honeycomb-shaped neutral coordination polymers (CPs). Between the adjacent lamellar structures in I and II, there exist π–π interactions between the pyridine rings belonging to phenanthroline of NCP{sup −} which stabilize the frameworks. Both I and II display stronger fluorescence emissions as well as high thermal stability. - Graphical abstract: One-dimensional nanotubular channels with the cross dimension of 37.1959(20)×23.6141(11)Å{sup 2} in the three-dimensional honeycomb-shaped coordination network of II are observed. The topological analysis of II indicates that there exists a typical diamond framework possessing large adamantanoid cages, which containing four cyclohexane-shaped patterns in chair conformations. - Highlights: • Two isomorphous and isostructural coordination polymers based on flexible ligand and two alkaline-earth metal salts have been synthesized and characterized. • Structural analysis indicates that I and II are assembled into 3D porous honeycomb-shaped metal-organic frameworks. • Both I and II display stronger fluorescence emissions and higher thermal stability.

  16. The synthesis and crystal structures of the first rare-earth alkaline-earth selenite chlorides MNd 10(SeO 3) 12Cl 8 ( M=Ca and Sr)

    NASA Astrophysics Data System (ADS)

    Berdonosov, P. S.; Olenev, A. V.; Dolgikh, V. A.; Lightfoot, P.

    2007-11-01

    Two new alkaline-earth Nd selenite chlorides MNd 10(SeO 3) 12Cl 8 ( M=Ca, Sr) were obtained using crystal growth from alkaline-earth chloride melts in quartz tubes. These new compounds crystallize in the orthorhombic system in space group C cca (#68). The compounds were studied by energy dispersive X-ray spectroscopy (EDX) and X-ray diffraction. It was shown that both compounds adopt the same structure type, constructed by complex [M 11(SeO 3) 12] 8+ slabs separated by chloride anion layers perpendicular to the longest cell parameter. The SeO 3 groups show a pyramidal shape and may be described as SeO 3E tetrahedra. Such SeO 3 groups decorate the Nd-O skeletons forming the [M 11(SeO 3) 12] 8+ slabs.

  17. New synthesis route for ternary transition metal amides as well as ultrafast amide-hydride hydrogen storage materials.

    PubMed

    Cao, Hujun; Santoru, Antonio; Pistidda, Claudio; Richter, Theresia M M; Chaudhary, Anna-Lisa; Gizer, Gökhan; Niewa, Rainer; Chen, Ping; Klassen, Thomas; Dornheim, Martin

    2016-04-14

    K2[Mn(NH2)4] and K2[Zn(NH2)4] were successfully synthesized via a mechanochemical method. The mixture of K2[Mn(NH2)4] and LiH showed excellent rehydrogenation properties. In fact, after dehydrogenation K2[Mn(NH2)4]-8LiH fully rehydrogenates within 60 seconds at ca. 230 °C and 5 MPa of H2. This is one of the fastest rehydrogenation rates in amide-hydride systems known to date. This work also shows a strategy for the synthesis of transition metal nitrides by decomposition of the mixtures of M[M'(NH2)n] (where M is an alkali or alkaline earth metal and M' is a transition metal) and metal hydrides.

  18. High-pressure densified solid solutions of alkaline earth hexaborides (Ca/Sr, Ca/Ba, Sr/Ba) and their high-temperature thermoelectric properties

    SciTech Connect

    Gürsoy, M.; Takeda, M.; Albert, B.

    2015-01-15

    Solid solutions of alkaline earth hexaborides were synthesized and densified by spark plasma sintering at 100 MPa. The high-temperature thermoelectric properties (Seebeck coefficients, electrical and thermal diffusivities, heat capacities) were measured between room temperature and 1073 K. CaB{sub 6}, SrB{sub 6}, BaB{sub 6} and the ternary hexaborides Ca{sub x}Sr{sub 1−x}B{sub 6}, Ca{sub x}Ba{sub 1−x}B{sub 6}, Sr{sub x}Ba{sub 1−x}B{sub 6} (x = 0.25, 0.5, 0.75) are n-type conducting compounds over the whole compositional and thermal ranges. The values of the figure of merit ZT for CaB{sub 6} (ca. 0.3 at 1073 K) were found to be significantly increased compared to earlier investigations which is attributed to the densification process. - Highlights: • Solid solutions of alkaline earth hexaborides were synthesized. • High-temperature thermoelectric properties of mixed calcium borides are excellent. • Spark plasma source densification results in high ZT values. • Borides are rare-earth free and refractory materials.

  19. Removal of toxic and alkali/alkaline earth metals during co-thermal treatment of two types of MSWI fly ashes in China.

    PubMed

    Yu, Jie; Qiao, Yu; Jin, Limei; Ma, Chuan; Paterson, Nigel; Sun, Lushi

    2015-12-01

    This study aims to vaporize heavy metals and alkali/alkaline earth metals from two different types of fly ashes by thermal treatment method. Fly ash from a fluidized bed incinerator (HK fly ash) was mixed with one from a grate incinerator (HS fly ash) in various proportions and thermally treated under different temperatures. The melting of HS fly ash was avoided when treated with HK fly ash. Alkali/alkaline earth metals in HS fly ash served as Cl-donors to promote the vaporization of heavy metals during thermal treatment. With temperature increasing from 800 to 900°C, significant amounts of Cl, Na and K were vaporized. Up to 1000°C in air, less than 3% of Cl and Na and less than 5% of K were retained in ash. Under all conditions, Cd can be vaporized effectively. The vaporization of Pb was mildly improved when treated with HS fly ash, while the effect became less pronounced above 900°C. Alkali/alkaline earth metals can promote Cu vaporization by forming copper chlorides. Comparatively, Zn vaporization was low and only slightly improved by HS fly ash. The low vaporization of Zn could be caused by the formation of Zn2SiO4, ZnFe2O4 and ZnAl2O4. Under all conditions, less than 20% of Cr was vaporized. In a reductive atmosphere, the vaporization of Cd and Pb were as high as that in oxidative atmosphere. However, the vaporization of Zn was accelerated and that of Cu was hindered because the formation of Zn2SiO4, ZnFe2O4 and ZnAl2O4 and copper chloride was depressed in reductive atmosphere.

  20. Identifying calcium sources at an acid deposition-impacted spruce forest: A strontium isotope, alkaline earth element multi-tracer approach

    USGS Publications Warehouse

    Bullen, T.D.; Bailey, S.W.

    2005-01-01

    Depletion of calcium from forest soils has important implications for forest productivity and health. Ca is available to fine feeder roots from a number of soil organic and mineral sources, but identifying the primary source or changes of sources in response to environmental change is problematic. We used strontium isotope and alkaline earth element concentration ratios of trees and soils to discern the record of Ca sources for red spruce at a base-poor, acid deposition-impacted watershed. We measured 87Sr/86Sr and chemical compositions of cross-sectional stemwood cores of red spruce, other spruce tissues and sequential extracts of co-located soil samples. 87Sr/86Sr and Sr/Ba ratios together provide a tracer of alkaline earth element sources that distinguishes the plant-available fraction of the shallow organic soils from those of deeper organic and mineral soils. Ca/Sr ratios proved less diagnostic, due to within-tree processes that fractionate these elements from each other. Over the growth period from 1870 to 1960, 87Sr/86Sr and Sr/Ba ratios of stemwood samples became progressively more variable and on average trended toward values that considered together are characteristic of the uppermost forest floor. In detail the stemwood chemistry revealed an episode of simultaneous enhanced uptake of all alkaline earth elements during the growth period from 1930 to 1960, coincident with reported local and regional increases in atmospheric inputs of inorganic acidity. We attribute the temporal trends in stemwood chemistry to progressive shallowing of the effective depth of alkaline earth element uptake by fine roots over this growth period, due to preferential concentration of fine roots in the upper forest floor coupled with reduced nutrient uptake by roots in the lower organic and upper mineral soils in response to acid-induced aluminum toxicity. Although both increased atmospheric deposition and selective weathering of Ca-rich minerals such as apatite provide possible

  1. Electronic structure, optical properties and bonding in alkaline earth halo-fluoride scintillators: BaClF, BaBrF and BaIF

    SciTech Connect

    Yedukondalu, N.; Babu, K. Ramesh; Bheemalingam, Ch.; Singh, David J; Vaitheeswaran, G.; Kanchana, V.

    2011-01-01

    We report first-principles studies of the structural, electronic, and optical properties of the alkaline-earth halofluorides, BaXF (X = Cl, Br, and I), including pressure dependence of structural properties. The band structures show clear separation of the halogen p derived valence bands into higher binding energy F and lower binding energy X derived manifolds reflecting the very high electronegativity of F relative to the other halogens. Implications of this for bonding and other properties are discussed. We find an anisotropic behavior of the structural parameters especially of BaIF under pressure. The optical properties on the other hand are almost isotropic, in spite of the anisotropic crystal structures.

  2. 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.

  3. Identifying the presence of a disulfide linkage in peptides by the selective elimination of hydrogen disulfide from collisionally activated alkali and alkaline earth metal complexes.

    PubMed

    Kim, Hugh I; Beauchamp, J L

    2008-01-30

    We report a new method for identifying disulfide linkages in peptides using mass spectrometry. This is accomplished by collisional activation of singly charged cationic alkali and alkaline earth metal complexes, which results in the highly selective elimination of hydrogen disulfide (H2S2). Complexes of peptides possessing disulfide bonds with sodium and alkaline earth metal are generated using electrospray ionization (ESI). Isolation followed by collision induced dissociation (CID) of singly charged peptide complexes results in selective elimination of H2S2 to leave newly formed dehydroalanine residues in the peptide. Further activation of the product yields sequence information in the region previously short circuited by the disulfide bond. For example, singly charged magnesium and calcium ion bound complexes of [Lys8]-vasopressin exhibit selective elimination of H2S2 via low-energy CID. Further isolation of the product followed by CID yields major b- and z-type fragments revealing the peptide sequence in the region between the newly formed dehydroalanine residues. Numerous model peptides provide mechanistic details for the selective elimination of H2S2. The process is initiated starting with a metal stabilized enolate anion at Cys, followed by cleavage of the S-C bond. An examination of the peptic digest of insulin provides an example of the application of the selective elimination of H2S2 for the identification of peptides with disulfide linkages. The energetics and mechanisms of H2S2 elimination from model compounds are investigated using density functional theory (DFT) calculations.

  4. Indirect ultraviolet detection of alkaline earth metal ions using an imidazolium ionic liquid as an ultraviolet absorption reagent in ion chromatography.

    PubMed

    Liu, Yong-Qiang; Yu, Hong

    2017-02-20

    A convenient and versatile method was developed for the separation and detection of alkaline earth metal ions by ion chromatography with indirect UV detection. The chromatographic separation of Mg(2+) , Ca(2+) , and Sr(2+) was performed on a carboxylic acid base cation exchange column using imidazolium ionic liquid/acid as the mobile phase, in which the imidazolium ionic liquid acted as an UV-absorption reagent. The effects of imidazolium ionic liquids, detection wavelength, acids in the mobile phase, and column temperature on the retention of Mg(2+) , Ca(2+) , and Sr(2+) were investigated. The main factors influencing the separation and detection were the background UV absorption reagent and the concentration of hydrogen ion in ion chromatography with indirect UV detection. The successful separation and detection of Mg(2+) , Ca(2+) , and Sr(2+) within 14 min were achieved using the selected chromatographic conditions, and the detection limits (S/N = 3) were 0.06, 0.12, and 0.23 mg/L, respectively. A new separation and detection method of alkaline earth metal ions by ion chromatography with indirect UV detection was developed, and the application range of ionic liquids was expanded.

  5. Origin of low sodium capacity in graphite and generally weak substrate binding of Na and Mg among alkali and alkaline earth metals.

    PubMed

    Liu, Yuanyue; Merinov, Boris V; Goddard, William A

    2016-04-05

    It is well known that graphite has a low capacity for Na but a high capacity for other alkali metals. The growing interest in alternative cation batteries beyond Li makes it particularly important to elucidate the origin of this behavior, which is not well understood. In examining this question, we find a quite general phenomenon: among the alkali and alkaline earth metals, Na and Mg generally have the weakest chemical binding to a given substrate, compared with the other elements in the same column of the periodic table. We demonstrate this with quantum mechanics calculations for a wide range of substrate materials (not limited to C) covering a variety of structures and chemical compositions. The phenomenon arises from the competition between trends in the ionization energy and the ion-substrate coupling, down the columns of the periodic table. Consequently, the cathodic voltage for Na and Mg is expected to be lower than those for other metals in the same column. This generality provides a basis for analyzing the binding of alkali and alkaline earth metal atoms over a broad range of systems.

  6. Origin of low sodium capacity in graphite and generally weak substrate binding of Na and Mg among alkali and alkaline earth metals

    NASA Astrophysics Data System (ADS)

    Liu, Yuanyue; Merinov, Boris V.; Goddard, William A., III

    2016-04-01

    It is well known that graphite has a low capacity for Na but a high capacity for other alkali metals. The growing interest in alternative cation batteries beyond Li makes it particularly important to elucidate the origin of this behavior, which is not well understood. In examining this question, we find a quite general phenomenon: among the alkali and alkaline earth metals, Na and Mg generally have the weakest chemical binding to a given substrate, compared with the other elements in the same column of the periodic table. We demonstrate this with quantum mechanics calculations for a wide range of substrate materials (not limited to C) covering a variety of structures and chemical compositions. The phenomenon arises from the competition between trends in the ionization energy and the ion-substrate coupling, down the columns of the periodic table. Consequently, the cathodic voltage for Na and Mg is expected to be lower than those for other metals in the same column. This generality provides a basis for analyzing the binding of alkali and alkaline earth metal atoms over a broad range of systems.

  7. Effect of metal cation replacement on the electronic structure of metalorganic halide perovskites: Replacement of lead with alkaline-earth metals

    NASA Astrophysics Data System (ADS)

    Pazoki, Meysam; Jacobsson, T. Jesper; Hagfeldt, Anders; Boschloo, Gerrit; Edvinsson, Tomas

    2016-04-01

    Organic and inorganic lead halogen perovskites, and in particular, C H3N H3Pb I3 , have during the last years emerged as a class of highly efficient solar cell materials. Herein we introduce metalorganic halogen perovskite materials for energy-relevant applications based on alkaline-earth metals. Based on the classical notion of Goldschmidt's rules and quantum mechanical considerations, the three alkaline-earth metals, Ca, Sr, and Ba, are shown to be able to exchange lead in the perovskite structure. The three alkaline-earth perovskites, C H3N H3Ca I3,C H3N H3Sr I3 , and C H3N H3Ba I3 , as well as the reference compound, C H3N H3Pb I3 , are in this paper investigated with density functional theory (DFT) calculations, which predict these compounds to exist as stable perovskite materials, and their electronic properties are explored. A detailed analysis of the projected molecular orbital density of states and electronic band structure from DFT calculations were used for interpretation of the band-gap variations in these materials and for estimation of the effective masses of the electrons and holes. Neglecting spin-orbit effects, the band gap of MACa I3,MASr I3 , and MABa I3 were estimated to be 2.95, 3.6, and 3.3 eV, respectively, showing the relative change expected for metal cation exchange. The shifts in the conduction band (CB) edges for the alkaline-earth perovskites were quantified using scalar relativistic DFT calculations and tight-binding analysis, and were compared to the situation in the more extensively studied lead halide perovskite, C H3N H3Pb I3 , where the change in the work function of the metal is the single most important factor in tuning the CB edge and band gap. The results show that alkaline-earth-based organometallic perovskites will not work as an efficient light absorber in photovoltaic applications but instead could be applicable as charge-selective contact materials. The rather high CB edge and the wide band gap together with the large

  8. Synthesis of ruthenium hydride

    NASA Astrophysics Data System (ADS)

    Kuzovnikov, M. A.; Tkacz, M.

    2016-02-01

    Ruthenium hydride was synthesized at a hydrogen pressure of about 14 GPa in a diamond-anvil cell. Energy-dispersive x-ray diffraction was used to monitor the ruthenium crystal structure as a function of hydrogen pressure up to 30 GPa. The hydride formation was accompanied by phase transition from the original hcp structure of the pristine metal to the fcc structure. Our results confirmed the theoretical prediction of ruthenium hydride formation under hydrogen pressure. The standard Gibbs free energy of the ruthenium hydride formation reaction was calculated assuming the pressure of decomposition as the equilibrium pressure.

  9. Alkaline earth imidazolate coordination polymers by solvent free melt synthesis as potential host lattices for rare earth photoluminescence: (x)(∞)[AE(Im)2(ImH)(2-3)], Mg, Ca, Sr, Ba, x = 1-2.

    PubMed

    Zurawski, Alexander; Rybak, J-Christoph; Meyer, Larissa V; Matthes, Philipp R; Stepanenko, Vladimir; Dannenbauer, Nicole; Würthner, Frank; Müller-Buschbaum, Klaus

    2012-04-14

    The series of alkaline earth elements magnesium, calcium, strontium and barium yields single crystalline imidazolate coordination polymers by reactions of the metals with a melt of 1H-imidazole: (1)(∞)[Mg(Im)(2)(ImH)(3)] (1), (2)(∞)[AE(Im)(2)(ImH)(2)], AE = Ca (2), Sr (3), and (1)(∞)[Ba(Im)(2)(ImH)(2)] (4). No additional solvents were used for the reactions. Co-doping experiments by addition of the rare earth elements cerium, europium and terbium were carried out. They indicate (2)(∞)[Sr(Im)(2)(ImH)(2)] as a possible host lattice for cerium(III) photoluminescence showing a blue emission and thus a novel blue emitting hybrid material phosphor 3:Ce(3+). Co-doping with europium and terbium is also possible but resulted in formation of (3)(∞)[Sr(Im)(2)]:Ln, Ln = Eu and Tb (5), with both exhibiting green emission of either Eu(2+) or Tb(3+). The other alkaline earth elements do not show acceptance of the rare earth ions investigated and a different structural chemistry. For magnesium and barium one-dimensional strand structures are observed whereas calcium and strontium give two-dimensional network structures. Combined with an increase of the ionic radii of AE(2+) the coordinative demand is also increasing from Mg(2+) to Ba(2+), reflected by four different crystal structures for the four elements Mg, Ca, Sr, Ba in 1-4. Different linkages of the imidazolate ligands result in a change from complete σ-N coordination in 1 to additional η(5)-π coordination in 4. The success of co-doping with different lanthanide ions is based on a match in the chemical behaviour and cationic radii. The use of strontium for host lattices with imidazole is a rare example in coordination chemistry of co-doping with small amounts of luminescence centers and successfully reduces the amount of high price rare earth elements in hybrid materials while maintaining the properties. All compounds are examples of pure N-coordinated coordination polymers of the alkaline earth metals and were

  10. Hysteresis in Metal Hydrides.

    ERIC Educational Resources Information Center

    Flanagan, Ted B., And Others

    1987-01-01

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

  11. 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.

  12. Dispersion coefficients for the interactions of the alkali-metal and alkaline-earth-metal ions and inert-gas atoms with a graphene layer

    NASA Astrophysics Data System (ADS)

    Kaur, Kiranpreet; Arora, Bindiya; Sahoo, B. K.

    2015-09-01

    Largely motivated by a number of applications, the van der Waals dispersion coefficients C3 of the alkali-metal ions Li+,Na+,K+, and Rb+, the alkaline-earth-metal ions Ca+,Sr+,Ba+, and Ra+, and the inert-gas atoms He, Ne, Ar, and Kr with a graphene layer are determined precisely within the framework of the Dirac model. For these calculations, we evaluate the dynamic polarizabilities of the above atomic systems very accurately by evaluating the transition matrix elements employing relativistic many-body methods and using the experimental values of the excitation energies. The dispersion coefficients are given as functions of the separation distance of an atomic system from the graphene layer and the ambiance temperature during the interactions. For easy extraction of these coefficients, we give a logistic fit to the functional forms of the dispersion coefficients in terms of the separation distances at room temperature.

  13. Low pressure ion chromatography with a low cost paired emitter-detector diode based detector for the determination of alkaline earth metals in water samples.

    PubMed

    Barron, Leon; Nesterenko, Pavel N; Diamond, Dermot; O'Toole, Martina; Lau, King Tong; Paull, Brett

    2006-09-01

    The use of a low pressure ion chromatograph based upon short (25 mm x 4.6 mm) surfactant coated monolithic columns and a low cost paired emitter-detector diode (PEDD) based detector, for the determination of alkaline earth metals in aqueous matrices is presented. The system was applied to the separation of magnesium, calcium, strontium and barium in less than 7min using a 0.15M KCl mobile phase at pH 3, with post-column reaction detection at 570 nm using o-cresolphthalein complexone. A comparison of the performance of the PEDD detector with a standard laboratory absorbance detector is shown, with limits of detection for magnesium and calcium using the low cost PEDD detector equal to 0.16 and 0.23 mg L(-1), respectively. Finally, the developed system was used for the determination of calcium and magnesium in a commercial spring water sample.

  14. Alkaline earth metal-based metal-organic framework: hydrothermal synthesis, X-ray structure and heterogeneously catalyzed Claisen-Schmidt reaction.

    PubMed

    Saha, Debraj; Maity, Tanmoy; Koner, Subratanath

    2014-09-14

    Two alkaline earth metal-based carboxylate systems, [Mg(HL)(H2O)2]n (1) and [Ca(H2L)2]n (2) (H3L = chelidamic acid) have been hydrothermally synthesized, and characterized by single-crystal X-ray diffraction, IR, elemental analysis, and thermo-gravimetric analysis. Compound 1 has a 2D structure incorporating two water molecules. The dehydrated species, 1a, generated from 1 by removal of the coordinated water, has been characterized by thermo-gravimetric analysis, IR, elemental analysis and variable temperature powder X-ray diffraction. Both 1 and its dehydrated species 1a catalyze the Claisen-Schmidt reaction under heterogeneous conditions, but 1a is a more effective catalyst under environmentally friendly conditions. The catalyst can readily be recovered and reused in successive cycles without detectable loss of activity. Compound 2 has a 3D structure and is thermally stable up to 540 °C, but is inactive catalytically.

  15. Calculation of thermodynamic potentials with the inclusion of fractional occupation numbers and investigation of FCC-BCC structural phase transitions in alkaline-earth metals

    NASA Astrophysics Data System (ADS)

    Pozhivatenko, V. V.

    2013-10-01

    The smearing near the Fermi level has been taken into account in the calculations of the thermodynamic characteristics of metals in order to improve the convergence of the performed calculations and to increase the quality of the obtained results. The choice of the smearing parameter usually has not been explained, although the results of the calculations differ significantly for different values of this parameter. Possible schemes for calculating the thermodynamic potentials with the inclusion of the smearing parameter and additional parameters of the volume and energy shifts have been considered. The influence of these parameters on the calculations of the thermodynamic properties of alkaline-earth metals under pressure and on the description of the structural phase transition has been analyzed.

  16. The coordination complex structures and hydrogen bonding in the three-dimensional alkaline earth metal salts (Mg, Ca, Sr and Ba) of (4-aminophenyl)arsonic acid.

    PubMed

    Smith, Graham; Wermuth, Urs D

    2017-01-01

    (4-Aminophenyl)arsonic acid (p-arsanilic acid) is used as an antihelminth in veterinary applications and was earlier used in the monosodium salt dihydrate form as the antisyphilitic drug atoxyl. Examples of complexes with this acid are rare. The structures of the alkaline earth metal (Mg, Ca, Sr and Ba) complexes with (4-aminophenyl)arsonic acid (p-arsanilic acid) have been determined, viz. hexaaquamagnesium bis[hydrogen (4-aminophenyl)arsonate] tetrahydrate, [Mg(H2O)6](C6H7AsNO3)·4H2O, (I), catena-poly[[[diaquacalcium]-bis[μ2-hydrogen (4-aminophenyl)arsonato-κ(2)O:O']-[diaquacalcium]-bis[μ2-hydrogen (4-aminophenyl)arsonato-κ(2)O:O

  17. Adsorption of alkali, alkaline-earth, simple and 3d transition metal, and nonmetal atoms on monolayer MoS{sub 2}

    SciTech Connect

    Li, X. D.; Fang, Y. M.; Wu, S. Q. E-mail: wsq@xmu.edu.cn; Zhu, Z. Z. E-mail: wsq@xmu.edu.cn

    2015-05-15

    Single adsorption of different atoms on pristine two-dimensional monolayer MoS{sub 2} have been systematically investigated by using density functional calculations with van der Waals correction. The adatoms cover alkali metals, alkaline earth metals, main group metal, 3d-transition metals, coinage metal and nonmetal atoms. Depending on the adatom type, metallic, semimetallic or semiconducting behavior can be found in direct bandgap monolayer MoS{sub 2}. Additionally, local or long-range magnetic moments of two-dimensional MoS{sub 2} sheet can also attained through the adsorption. The detailed atomic-scale knowledge of single adsorption on MoS{sub 2} monolayer is important not only for the sake of a theoretical understanding, but also device level deposition technological application.

  18. Determination of rare earth elements, uranium and thorium in geological samples by ICP-MS, using an automatic fusion machine as an alkaline digestion tool.

    NASA Astrophysics Data System (ADS)

    Granda, Luis; Rivera, Maria; Velasquez, Colon; Barona, Diego; Carpintero, Natalia

    2014-05-01

    At the present time, rare earth elements deposits have became in strategic resources for extraction of raw materials in order to manufacture high tech devices (computers, LCD, cell phones, batteries for hybrid vehicles, fiber optics and wind turbines) (1).The appropriate analytical determination of the REE ( rare earth elements) in sediment and rock samples , is important to find potential deposits and to recognize geological environments for identifying possible alterations and mineral occurrences. The alkaline fusion, which aim is to move the entire sample from solid to liquid state by forming water soluble complexes of boron and lithium, as a previous procedure for the determination of these elements, usually takes a lot of time due to the complexity of the analysis phase and by the addition of other reagents (Tm and HF ) (2) to compensate the lack of strict temperature control. The objective of this work is to develop an efficient alternative to alkaline digestion using an electrical fusion machine, which allows to create temperature programs with advanced process control and supports up to 5 samples simultaneously, which generates a reproducibility of the method and results during the melting step. Additionally, this new method permits the processing of a larger number of samples in a shorter time. The samples analyzed in this method were weighed into porcelain crucibles and subjected to calcination for 4 hours at 950 ° C in order to determine the Lost on Ignition (LOI ) , that serves to adjust the analytical results and to preserve the shelf life of the platinum ware. Subsequently, a fraction of the calcined sample was weighed into platinum crucibles and mixed with ultra-pure lithium metaborate ( flux ) 1:4 . The crucible was then placed in the fusion machine, which was programmed to take the sample from room temperature to 950 ° C in five minutes, make a small ramp to 970 ° C maintain that temperature for five minutes and download the melt in a 10 % v / v

  19. Syntheses and characterization of energetic compounds constructed from alkaline earth metal cations (Sr and Ba) and 1,2-bis(tetrazol-5-yl)ethane

    SciTech Connect

    Xia Zhengqiang; Chen Sanping; Wei Qing; Qiao Chengfang

    2011-07-15

    Two new energetic compounds, [M(BTE)(H{sub 2}O){sub 5}]{sub n} (M=Sr(1), Ba(2)) [H{sub 2}BTE=1,2-bis(tetrazol-5-yl)ethane], have been hydrothermally synthesized and structurally characterized. Single-crystal X-ray diffraction analyses reveal that they are isomorphous and exhibit 2D (4,4) net framework, generated by 4-connected Sr{sub 2}(H{sub 2}O){sub 10}/Ba{sub 2}(H{sub 2}O){sub 10} SBUs linked up by two independent binding modes of H{sub 2}BTE, and the resulting 2D structure is interconnected by hydrogen-bond and strong face to face {pi}-{pi} stacking interactions between two tetrazole rings to lead to a 3D supramolecular architecture. DSC measurements show that they have significant catalytic effects on thermal decomposition of ammonium perchlorate. Moreover, the photoluminescence properties, thermogravimetric analyses, and flame colors of the as-prepared compounds are also investigated in this paper. - Graphical abstract: Two novel 2D isomorphous alkaline earth metal complexes were assembled by 4-connected Sr{sub 2}(H{sub 2}O){sub 10}/Ba{sub 2}(H{sub 2}O){sub 10} SBUs and two independent binding modes of H{sub 2}BTE ligands, and the catalytic performances toward thermal decomposition of ammonium perchlorate and photoluminescent properties of them were investigated. Highlights: > Two novel alkaline earth energetic coordination polymers have been prepared.{yields} Both structures are layered based on 4-connected Sr{sub 2}(H{sub 2}O){sub 10}/Ba{sub 2}(H{sub 2}O){sub 10} SBUs and two distinct H{sub 2}BTE coordination modes.{yields} The dehydrated products of the compounds possess good thermostability and significant catalytic effects on thermal decomposition of AP.

  20. 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.

  1. Chemistry of intermetallic hydrides

    SciTech Connect

    Reilly, J.J.

    1991-01-01

    Certain intermetallic hydrides are safe, convenient and inexpensive hydrogen storage compounds. A particular advantage of such compounds is the ease with which their properties can be modified by small changes in alloy composition or preparation. This quality can be exploited to optimize their storage properties for particular applications, e.g. as intermetallic hydride electrodes in batteries. We will be concerned herein with the more important aspects of the thermodynamic and structural principles which regulate the behavior of intermetallic hydrogen systems and then illustrate their application using the archetype hydrides of LaNi5, FeTi and Mg alloys. The practical utility of these classes of materials will be briefly noted.

  2. Rapid hydrolysis of model phosphate diesters by alkaline-earth cations in aqueous DMSO: speciation and kinetics.

    PubMed

    Taran, Olga; Medrano, Felipe; Yatsimirsky, Anatoly K

    2008-12-14

    Kinetics of the cleavage of two phosphate diesters, bis(4-nitrophenyl) phosphate and 2-hydroxypropyl 4-nitrophenyl phosphate and a triester, 4-nitrophenyl diphenyl phosphate, in the presence of Mg(II), Ca(II) and Sr(II) were studied in 90% vol. DMSO at 37 degrees C. The alkaline hydrolysis of the triester was inhibited by all cations, but with both phosphodiesters strong catalytic effects were observed. Potentiometric titrations of metal perchlorates by Bu4N(OH) revealed formation of M2(OH)3+, M(OH)+, M(OH)2 and M2(OH)5- species. Rate constants for phosphodiester cleavage by individual species were obtained from analysis of rate-concentration profiles. Observed first-order rate constants in the presence of 1-2 mM Mg(II) or Ca(II) in neutral and weakly basic solutions were 10(8)-10(11) times higher than those for background hydrolysis at the same pH while in water additions of up to 50 mM metal produced <100-fold accelerations. Possible structures of DMSO solvated catalyst-substrate complexes were modeled by DFT calculations with Mg(II). The increased catalytic activity in 90% DMSO is attributed to stronger association of hydroxide ions and anionic phosphodiesters with metal ions and to preferable solvation of cations by DMSO, which creates favorable for reaction anhydrous microenvironment in the coordination sphere of the catalyst.

  3. 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.

  4. 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.

  5. Lack of marked cyto- and genotoxicity of cristobalite in devitrified (heated) alkaline earth silicate wools in short-term assays with cultured primary rat alveolar macrophages.

    PubMed

    Ziemann, Christina; Harrison, Paul T C; Bellmann, Bernd; Brown, Robert C; Zoitos, Bruce K; Class, Philippe

    2014-02-01

    Alkaline earth silicate (AES) wools are low-biopersistence high-temperature insulation wools. Following prolonged periods at high temperatures they may devitrify, producing crystalline silica (CS) polymorphs, including cristobalite, classified as carcinogenic to humans. Here we investigated the cytotoxic and genotoxic significance of cristobalite present in heated AES wools. Primary rat alveolar macrophages were incubated in vitro for 2 h with 200 µg/cm² unheated/heated calcium magnesium silicate wools (CMS1, CMS2, CMS3; heat-treated for 1 week at, or 4 weeks 150 °C below, their respective classification temperatures) or magnesium silicate wool (MS; heated for 24 h at 1260 °C). Types and quantities of CS formed, and fiber size distribution and shape were determined by X-ray diffraction and electron microscopy. Lactate dehydrogenase release and alkaline and hOGG1-modified comet assays were used, ± aluminum lactate (known to quench CS effects), for cytotoxicity/genotoxicity screening. Cristobalite content of wools increased with heating temperature and duration, paralleled by decreases in fiber length and changes in fiber shape. No marked cytotoxicity, and nearly no (CMS) or only slight (MS) DNA-strand break induction was observed, compared to the CS-negative control Al₂O₃, whereas DQ12 as CS-positive control was highly active. Some samples induced slight oxidative DNA damage, but no biological endpoint significantly correlated with free CS, quartz, or cristobalite. In conclusion, heating of AES wools mediates changes in CS content and fiber length/shape. While changes in fiber morphology can impact biological activity, cristobalite content appears minor or of no relevance to the intrinsic toxicity of heated AES wools in short-term assays with rat alveolar macrophages.

  6. Nickel metal hydride LEO cycle testing

    NASA Technical Reports Server (NTRS)

    Lowery, Eric

    1995-01-01

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

  7. Coordination chemistry of the alkaline earth metal ions with Zwitterionic forms of the Schift bases. X-Ray studies and other spectroscopic properties

    NASA Astrophysics Data System (ADS)

    Tajmir-Riahi, H. A.; Lotfipoor, M.

    The non-ionized forms of tetradentate Schiff bases NN'-ethylenebis(salicylideneimine), H 2L and NN'-propane-1,3-diylbis(salicylideneimine), H 2L' react with hydrated alkaline earth halide and nitrate to give complexes of the type: M(H 2L)Cl 2· nH 2O [M = Mg(II), Ca(II), Sr(II); n = 0-4], M(H 2L) 2Cl 2 [M = Ca(II), Sr(II), M(H 2L) nBr 2 [M = Ca(II), Sr(II); n = 2, 3 and Mg 2(H 2L) 3Br 4], M(H 2L) nI 2 [M = Mg(II), Ca(II), Sr(II), Ba(II); n = 2, 3)], M(H 2L) n(NO 3) 2 and M(H 2L') n(NO 1) 2[M = Mg(II), Ca(II); n = 1, 2)]. Because of distinct spectral similarities with structurally known Ca(H 2L')(NO 3) 2 compound, the Schiff bases are coordinated through the negatively charged phenolic oxygen atoms and not the nitrogen atoms of the azomethine groups, which carry the protons transferred from phenolic groups on complexation. Halide and nitrate are coordinated to the central metal ion except in 2:1 nitrato complexes where the presence of both ionic and coordinated nitrate groups are evident and also in 3:1 halide complexes where the presence of non-coordinated halide cannot be excluded. X-Ray powder photographs showed no marked similarities between Ca(H 2L')(NO 3) 2 and Mg(H 2L')(NO 3) 2 while there are some isomorphic features between the same types of halide complexes. Infrared spectra and other structural information revealed the polymeric nature of the complexes. Therefore the coordination numbers exhibited by the alkaline earth metal cations would be 4, 6 or 8 in these series of Schiff base complexes.

  8. Dissolution stoichiometry and adsorption of alkali and alkaline earth elements to the acid-reacted wollastonite surface at 25°C

    NASA Astrophysics Data System (ADS)

    Xie, Zhixin; Walther, John V.

    1994-06-01

    The Ca 2+/H + exchange reaction on the wollastonite surface was investigated at 25°C with both short-term (<2.5 h) and long-term (>48 h) dissolution studies. In acidic solutions, the dissolution of wollastonite is nonstoichiometric with a greater release of Ca than Si relative to the wollastonite stoichiometry. Both short-term and long-term Ca 2+/H + exchange reaction stoichiometries are 0.5. Rapid desorption of Ca 2+ from the surface of untreated wollastonite caused a rise of the suspension pH to about 10 in a couple of minutes. Therefore, potentiometric titrations were performed with an acidreacted wollastonite where most surface detachable Ca 2+ had been removed. Addition of alkali and alkaline earth metal chloride solutions to the acid-reacted wollastonite suspension results in a pH decrease with K +> Na + > Ba 2+ > Mg 2+ > Ca 2+ in equal molal solutions. This suggests that the cations in these solutions are adsorbed to the wollastonite surface. Surface protonation properties of the acid-reacted wollastonite are found to be similar to those of microporous silica but with the point of zero salt effect (pzse) of 4.5-5.5 rather than the 3.0 of microporous silica. The surface protonation-deprotonation as a function of pH is modeled with a one-site double layer model which includes Na adsorption from the background electrolyte to reasonable accuracy. The adsorption of CrO 42-, MoO 42-, Ca 2+, Mg 2+, Ba 2+, and Na + from aqueous solutions to the acidreacted wollastonite/water interface was determined as a function of the pH and ionic strength of the solution. CrO 42- and MoO 42- were not adsorbed to the wollastonite surface at pH above 3. The extent of cation adsorption increases with increasing pH and decreases with increasing ionic strength. Ca 2+ adsorption depends on both the surface area of wollastonite and total amount of Ca 2+ in the suspension. For alkaline earth metals at the same concentration, the adsorption sequence is Ba 2+> Ca 2+> Mg 2+. At pH 8.5, the

  9. Lightweight hydride storage materials

    SciTech Connect

    Thomas, G.J.; Guthrie, S.E.; Bauer, W.

    1995-09-01

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

  10. The long-range non-additive three-body dispersion interactions for the rare gases, alkali, and alkaline-earth atoms.

    PubMed

    Tang, Li-Yan; Yan, Zong-Chao; Shi, Ting-Yun; Babb, James F; Mitroy, J

    2012-03-14

    The long-range non-additive three-body dispersion interaction coefficients Z(111), Z(112), Z(113), and Z(122) are computed for many atomic combinations using standard expressions. The atoms considered include hydrogen, the rare gases, the alkali atoms (up to Rb), and the alkaline-earth atoms (up to Sr). The term Z(111) arising from three mutual dipole interactions is known as the Axilrod-Teller-Muto coefficient or the DDD (dipole-dipole-dipole) coefficient. Similarly, the terms Z(112), Z(113), and Z(122) arise from the mutual combinations of dipole (1), quadrupole (2), and octupole (3) interactions between atoms and they are sometimes known, respectively, as dipole-dipole-quadrupole, dipole-dipole-octupole, and dipole-quadrupole-quadrupole coefficients. Results for the four Z coefficients are given for the homonuclear trimers, for the trimers involving two like-rare-gas atoms, and for the trimers with all combinations of the H, He, and Li atoms. An exhaustive compilation of all coefficients between all possible atomic combinations is presented as supplementary data.

  11. CO2 capture properties of alkaline earth metal oxides and hydroxides: A combined density functional theory and lattice phonon dynamics study

    NASA Astrophysics Data System (ADS)

    Duan, Yuhua; Sorescu, Dan C.

    2010-08-01

    By combining density functional theory and lattice phonon dynamics, the thermodynamic properties of CO2 absorption/desorption reactions with alkaline earth metal oxides MO and hydroxides M(OH)2 (where M=Be,Mg,Ca,Sr,Ba) are analyzed. The heats of reaction and the chemical potential changes of these solids upon CO2 capture reactions have been calculated and used to evaluate the energy costs. Relative to CaO, a widely used system in practical applications, MgO and Mg(OH)2 systems were found to be better candidates for CO2 sorbent applications due to their lower operating temperatures (600-700 K). In the presence of H2O, MgCO3 can be regenerated into Mg(OH)2 at low temperatures or into MgO at high temperatures. This transition temperature depends not only on the CO2 pressure but also on the H2O pressure. Based on our calculated results and by comparing with available experimental data, we propose a general computational search methodology which can be used as a general scheme for screening a large number of solids for use as CO2 sorbents.

  12. Heating temperature dependence of Cr(III) oxidation in the presence of alkali and alkaline earth salts and subsequent Cr(VI) leaching behavior.

    PubMed

    Verbinnen, Bram; Billen, Pieter; Van Coninckxloo, Michiel; Vandecasteele, Carlo

    2013-06-04

    In this paper, the temperature dependence of Cr(III) oxidation in high temperature processes and the subsequent Cr(VI) leaching was studied using synthetic mixtures. It was experimentally shown that in the presence of alkali and alkaline earth salts, oxidation of Cr(III) takes place, consistent with thermodynamic calculations. Heating of synthetic mixtures of Cr2O3 and Na, K, or Ca salts led to elevated leaching of Cr(VI); in the presence of Na, more than 80% of the initial Cr(III) amount was converted to Cr(VI) at 600-800 °C. Kinetic experiments allowed explanation of the increase in Cr(VI) leaching for increasing temperatures up to 600-800 °C. After reaching a maximum in Cr(VI) leaching at temperatures around 600-800 °C, the leaching decreased again, which could be explained by the formation of a glassy phase that prevents leaching of the formed Cr(VI). By way of illustration, Cr(VI) formation and leaching was evaluated for a case study, the fabrication of ceramic material from contaminated sludge. Based on the proposed reaction mechanisms, countermeasures to prevent Cr oxidation (addition of NH4H2PO4, heating under inert atmosphere) were proposed and successfully tested for synthetic mixtures and for the case study.

  13. Volatilisation of alkali and alkaline earth metallic species during the pyrolysis of biomass: differences between sugar cane bagasse and cane trash.

    PubMed

    Keown, Daniel M; Favas, George; Hayashi, Jun-ichiro; Li, Chun-Zhu

    2005-09-01

    Sugar cane bagasse and cane trash were pyrolysed in a novel quartz fluidised-bed/fixed-bed reactor. Quantification of the Na, K, Mg and Ca in chars revealed that pyrolysis temperature, heating rate, valence and biomass type were important factors influencing the volatilisation of these alkali and alkaline earth metallic (AAEM) species. Pyrolysis at a slow heating rate (approximately 10 K min(-1)) led to minimal (often <20%) volatilisation of AAEM species from these biomass samples. Fast heating rates (>1000 K s(-1)), encouraging volatile-char interactions with the current reactor configuration, resulted in the volatilisation of around 80% of Na, K, Mg and Ca from bagasse during pyrolysis at 900 degrees C. Similar behaviour was observed for monovalent Na and K with cane trash, but the volatilisation of Mg and Ca from cane trash was always restricted. The difference in Cl content between bagasse and cane trash was not sufficient to fully explain the difference in the volatilisation of Mg and Ca.

  14. Mechanochemical synthesis, structure, and properties of solid solutions of alkaline earth metal fluorides: Ma1-xMbxF2 (M: Ca, Sr, Ba)

    NASA Astrophysics Data System (ADS)

    Heise, M.; Scholz, G.; Düvel, A.; Heitjans, P.; Kemnitz, E.

    2016-10-01

    The capability of mechanochemical synthesis for the formation of solid solutions of alkaline earth metal fluorides Ma1-xMbxF2 (M: Ca, Sr, Ba) was tested by fluorination of metal acetates and metal hydroxides with ammonium fluoride directly at milling. Evidence was found for a mutual substitution of cations on their lattice positions in Ca1-xSrxF2 and Ba1-xSrxF2 samples. For the Ba/Ca-system this synthesis route is only partially successful. X-ray diffraction and 19F MAS NMR spectroscopy were used to characterize all samples concerning their crystal structure and local fluorine coordination. Calculations of 19F chemical shifts with the superposition model along with probability calculations for the intensity of the individual 19F lines, performed in dependence on the molar composition of the samples, perfectly agree with the experimental findings. The fluoride ion conductivity of as-prepared samples, determined by temperature dependent DC conductivity measurements, is significantly higher than those of crystalline binary fluorides. Moreover, a higher F- ion conductivity is observed for samples with higher mixing grade in the Ca/Sr-and the Ba/Sr-systems.

  15. Hydrated hydride anion clusters

    NASA Astrophysics Data System (ADS)

    Lee, Han Myoung; Kim, Dongwook; Singh, N. Jiten; Kołaski, Maciej; Kim, Kwang S.

    2007-10-01

    On the basis of density functional theory (DFT) and high level ab initio theory, we report the structures, binding energies, thermodynamic quantities, IR spectra, and electronic properties of the hydride anion hydrated by up to six water molecules. Ground state DFT molecular dynamics simulations (based on the Born-Oppenheimer potential surface) show that as the temperature increases, the surface-bound hydride anion changes to the internally bound structure. Car-Parrinello molecular dynamics simulations are also carried out for the spectral analysis of the monohydrated hydride. Excited-state ab initio molecular dynamics simulations show that the photoinduced charge-transfer-to-solvent phenomena are accompanied by the formation of the excess electron-water clusters and the detachment of the H radical from the clusters. The dynamics of the detachment process of a hydrogen radical upon the excitation is discussed.

  16. Phase I. Lanthanum-based Start Materials for Hydride Batteries

    SciTech Connect

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

    2013-08-20

    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 (La1-xRx)(Ni1-yMy)(Siz), 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.

  17. 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.

  18. 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.

  19. Interaction of Rydberg atoms in circular states with the alkaline-earth Ca(4s{sup 2}) and Sr(5s{sup 2}) atoms

    SciTech Connect

    Mironchuk, E. S.; Narits, A. A.; Lebedev, V. S.

    2015-11-15

    The resonant mechanism of interaction of alkaline-earth atoms having a low electron affinity to Rydberg atoms in circular (l = vertical bar m vertical bar = n–1) and near-circular states has been studied. To describe the dynamics of resonant processes accompanied by nonadiabatic transitions between ionic and Rydberg covalent terms of a quasimolecule, an approach based on the integration of coupled equations for the probability amplitudes has been developed taking into account the possibility of the decay of an anion in the Coulomb field of the positive ionic core of a highly excited atom. The approach involves the specific features of the problem associated with the structure of the wavefunction of a Rydberg electron in states with high orbital angular momenta l ∼ n–1. This approach provides a much more accurate description of the dynamics of electronic transitions at collisions between atoms than that within the modified semiclassical Landau–Zener model. In addition, this approach makes it possible to effectively take into account many channels of the problem. The cross sections for resonant quenching of Rydberg states of the Li(nlm) atom with given principal n, orbital l = n–1, and magnetic m quantum numbers at thermal collisions with the Ca(4s{sup 2}) and Sr(5s{sup 2}) atoms have been calculated. The dependences of the results on n, m, and angle α between the relative velocity of the atoms and the normal to the plane of the orbit of the Rydberg electron have been obtained. The influence of orientational effects on the efficiency of the collisional destruction of circular and near-circular states has been studied. The results indicate a higher stability of such states to their perturbations by neutral particles as compared to usually studied nl states with low values of l (l ≪ n)

  20. Fullerene-C60 and crown ether doped on C60 sensors for high sensitive detection of alkali and alkaline earth cations

    NASA Astrophysics Data System (ADS)

    Zaghmarzi, Fatemeh Alipour; Zahedi, Mansour; Mola, Adeleh; Abedini, Saboora; Arshadi, Sattar; Ahmadzadeh, Saeed; Etminan, Nazanin; Younesi, Omran; Rahmanifar, Elham; Yoosefian, Mehdi

    2017-03-01

    Fullerenes are effective acceptor components with high electron affinity for charge transfer. The significant influences of chemical adsorption of the cations on the electrical sensitivity of pristine C60 and 15-(C2H4O)5/C60 nanocages could be the basis of new generation of electronic sensor design. The density functional theory calculation for alkali and alkaline earth cations detection by pristine C60 and 15-(C2H4O)5/C60 nanocages are considered at B3LYP level of theory with 6-31 G(d) basis set. The quantum theory of atoms in molecules analysis have been performed to understand the nature of intermolecular interactions between the cations and nanocages. Also, the natural bond orbital analysis have been performed to assess the intermolecular interactions in detail. Furthermore, the frontier molecular orbital, energy gap, work function, electronegativity, number of transferred electron (∆N), dipole moment as well as the related chemical hardness and softness are investigated and calculated in this study. The results show that the adsorption of cations (M=Na+, K+, Mg2+ and Ca2+) are exothermic and the binding energy in pristine C60 nanocage and 15-(C2H4O)5/C60 increases with respect to the cations charge. The results also denote a decrease in the energy gap and an increase in the electrical conductivity upon the adsorption process. In order to validate the obtained results, the density of state calculations are employed and presented in the end as well.

  1. Unimolecular and hydrolysis channels for the detachment of water from microsolvated alkaline earth dication (Mg2+, Ca2+, Sr2+, Ba2+) clusters

    SciTech Connect

    Miliordos, Evangelos; Xantheas, Sotiris S.

    2014-02-07

    We examine theoretically the three channels that are associated with the detachment of a single water molecule from the aqueous clusters of the alkaline earth dications, [M(H2O)n]2+, M = Mg, Ca, Sr, Ba, n ≤ 6. These are the unimolecular water loss (M2+(H2O)n-1 + H2O) and the two hydrolysis channels resulting to the loss of hydronium ([MOH(H2O)n-2]+ + H3O+) and Zundel ([MOH(H2O)n-3]+ + H3O+(H2O)) cations. The Potential Energy Curves (PECs) corresponding to those three channels were constructed at the Møller-Plesset second order perturbation (MP2) level of theory with basis sets of double- and triple-ζ quality. We furthermore investigated the water and hydronium loss channels from the mono-hydroxide water clusters with up to four water molecules, [MOH(H2O)n]+, 1 ≤ n ≤ 4. Our results indicate the preference of the hydronium loss and possibly the Zundel cation loss channels for the smallest size clusters, whereas the unimolecular water loss channel is preferred for the larger ones as well as the mono-hydroxide clusters. Although the charge separation (hydronium and Zundel cation loss) channels produce more stable products when compared to the ones for the unimolecular water loss, they also require the surmounting of high energy barriers, a fact that makes the experimental observation of fragments related to these hydrolysis channels difficult.

  2. Absorption spectroscopy of heavy alkaline earth metals Ba and Sr in rare gas matrices—CCSD(T) calculations and atomic site occupancies

    SciTech Connect

    Davis, Barry M.; McCaffrey, John G.

    2016-01-28

    Isolation of the heavier alkaline earth metals Ba and Sr in the solid rare gases (RGs) Ar, Kr, and Xe is analysed with absorption spectroscopy and interpreted partly with the assistance of ab initio calculations of the diatomic M ⋅ RG ground state interaction potentials. The y{sup 1}P←a{sup 1}S resonance transitions in the visible spectral region are used to compare the isolation conditions of these two metal atom systems and calcium. Complex absorption bands were recorded in all three metal atom systems even after extensive sample annealing. Coupled cluster calculations conducted on the ground states of the nine M ⋅ RG diatomics (M = Ca, Sr, and Ba; RG = Ar, Kr, and Xe) at the coupled cluster single, double, and non-iterative triple level of theory revealed long bond lengths (>5 Å) and shallow bound regions (<130 cm{sup −1}). All of the M ⋅ RG diatomics have bond lengths considerably longer than those of the rare gas dimers, with the consequence that isolation of these metal atoms in a single substitutional site of the solid rare gas is unlikely, with the possible exception of Ca/Xe. The luminescence of metal dimer bands has been recorded for Ba and Sr revealing very different behaviours. Resonance fluorescence with a lifetime of 15 ns is observed for the lowest energy transition of Sr{sub 2} while this transition is quenched in Ba{sub 2}. This behaviour is consistent with the absence of vibrational structure on the dimer absorption band in Ba{sub 2} indicating lifetime broadening arising from efficient relaxation to low-lying molecular states. More extensive 2D excitation-emission data recorded for the complex site structures present on the absorption bands of the atomic Ba and Sr systems will be presented in future publications.

  3. Absorption spectroscopy of heavy alkaline earth metals Ba and Sr in rare gas matrices--CCSD(T) calculations and atomic site occupancies.

    PubMed

    Davis, Barry M; McCaffrey, John G

    2016-01-28

    Isolation of the heavier alkaline earth metals Ba and Sr in the solid rare gases (RGs) Ar, Kr, and Xe is analysed with absorption spectroscopy and interpreted partly with the assistance of ab initio calculations of the diatomic M ⋅ RG ground state interaction potentials. The y(1)P ← a(1)S resonance transitions in the visible spectral region are used to compare the isolation conditions of these two metal atom systems and calcium. Complex absorption bands were recorded in all three metal atom systems even after extensive sample annealing. Coupled cluster calculations conducted on the ground states of the nine M ⋅ RG diatomics (M = Ca, Sr, and Ba; RG = Ar, Kr, and Xe) at the coupled cluster single, double, and non-iterative triple level of theory revealed long bond lengths (>5 Å) and shallow bound regions (<130 cm(-1)). All of the M ⋅ RG diatomics have bond lengths considerably longer than those of the rare gas dimers, with the consequence that isolation of these metal atoms in a single substitutional site of the solid rare gas is unlikely, with the possible exception of Ca/Xe. The luminescence of metal dimer bands has been recorded for Ba and Sr revealing very different behaviours. Resonance fluorescence with a lifetime of 15 ns is observed for the lowest energy transition of Sr2 while this transition is quenched in Ba2. This behaviour is consistent with the absence of vibrational structure on the dimer absorption band in Ba2 indicating lifetime broadening arising from efficient relaxation to low-lying molecular states. More extensive 2D excitation-emission data recorded for the complex site structures present on the absorption bands of the atomic Ba and Sr systems will be presented in future publications.

  4. Characterization of Surface and Bulk Nitrates of γ-Al2O3-Supported Alkaline Earth Oxides using Density Functional Theory

    SciTech Connect

    Mei, Donghai; Ge, Qingfeng; Kwak, Ja Hun; Kim, Do Heui; Verrier, Christelle M.; Szanyi, Janos; Peden, Charles HF

    2009-05-14

    “Surface" and "bulk" nitrates formed on a series of alkaline earth oxides (AEOs), AE(NO3)2, were investigated using first-principles density functional theory calculations. The formation of these surface and bulk nitrates was modeled by the adsorption of NO2+NO3 pairs on gamma-Al2O3-supported monomeric AEOs (MgO, CaO, SrO, and BaO) and on the extended AEO(001) surfaces, respectively. The calculated vibrational frequencies of the surface and bulk nitrates based on our proposed models are in good agreement with experimental measurements of AEO/gamma-Al2O3 materials after prolonged NO2 exposure. This indicates that experimentally observed "surface" nitrates are most likely formed with isolated two dimensional (including monomeric) AEO clusters on the gamma-Al2O3 substrate, while the "bulk" nitrates are formed on exposed (including (001)) surfaces (and likely in the bulk as well) of large three dimensional AEO particles supported on the gamma-Al2O3 substrate. Also in line with the experiments, our calculations show that the low and high frequency components of the vibrations for both surface and bulk nitrates are systematically red shifted with the increasing basicity and cationic size of the AEOs. The adsorption strengths of NO2+NO3 pairs are nearly the same for the series of alumina-supported monomeric AEOs, while the adsorption strengths of NO2+NO3 pairs on the AEO surfaces increase in the order of MgO < CaO < SrO ~ BaO. Compared to the NO2+NO3 pair that only interacts with monomeric AEOs, the stability of NO2+NO3 pairs that interact with both the monomeric AEO and the gamma-Al2O3 substrate is enhanced by about 0.5 eV. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  5. Alkaline Earth Metal Zirconate Perovskites MZrO3 (M=Ba(2+), Sr(2+), Ca(2+)) Derived from Molecular Precursors and Doped with Eu(3+) Ions.

    PubMed

    Drąg-Jarząbek, Anna; John, Łukasz; Petrus, Rafał; Kosińska-Klähn, Magdalena; Sobota, Piotr

    2016-03-24

    The effect of alkaline earth metal alkoxides on the protonation of zirconocene dichloride was investigated. This approach enabled the design of compounds with preset molecular structures for generating high-purity binary metal oxide perovskites MZrO3 (M=Ba(2+), Sr(2+), Ca(2+)). Single-source molecular precursors [Ba4 Zr2 (μ6 -O)(μ3 ,η(2)-OR)8 (OR)2(η(2) -HOR)2 (HOR)2 Cl4], [Sr4 Zr2 (μ6 -O)(μ3 ,η(2)-OR)8 (OR)2 (HOR)4 Cl4], [Ca4 Zr2 (μ6-O)(μ3 ,η(2)-OR)8 (OR)2 Cl4], and [Ca6 Zr2 (μ2 ,η(2)-OR)12 (μ-Cl)2 (η(2) -HOR)4 Cl6 ]⋅8 CH2 Cl2 were prepared via elimination of the cyclopentadienyl ring from Cp2 ZrCl2 as CpH in the presence of M(OR)2 and alcohol ROH (ROH=CH3OCH2 CH2OH) as a source of protons. The resulting complexes were characterized by elemental analysis, IR and NMR spectroscopy, and single-crystal X-ray diffraction. The compounds were then thermally decomposed to MCl2 /MZrO3 mixtures. Leaching of MCl2 from the raw powder with deionized water produced highly pure perovskite-like oxide particles of 40-80 nm in size. Luminescence studies on Eu(3+)-doped MZrO3 revealed that the perovskites are attractive host lattices for potential applications in display technology.

  6. Selective trans-membrane transport of alkali and alkaline earth cations through graphene oxide membranes based on cation-π interactions.

    PubMed

    Sun, Pengzhan; Zheng, Feng; Zhu, Miao; Song, Zhigong; Wang, Kunlin; Zhong, Minlin; Wu, Dehai; Little, Reginald B; Xu, Zhiping; Zhu, Hongwei

    2014-01-28

    Graphene and graphene oxide (G-O) have been demonstrated to be excellent filters for various gases and liquids, showing potential applications in areas such as molecular sieving and water desalination. In this paper, the selective trans-membrane transport properties of alkali and alkaline earth cations through a membrane composed of stacked and overlapped G-O sheets ("G-O membrane") are investigated. The thermodynamics of the ion transport process reveal that the competition between the generated thermal motions and the interactions of cations with the G-O sheets results in the different penetration behaviors to temperature variations for the considered cations (K(+), Mg(2+), Ca(2+), and Ba(2+)). The interactions between the studied metal atoms and graphene are quantified by first-principles calculations based on the plane-wave-basis-set density functional theory (DFT) approach. The mechanism of the selective ion trans-membrane transportation is discussed further and found to be consistent with the concept of cation-π interactions involved in biological systems. The balance between cation-π interactions of the cations considered with the sp(2) clusters of G-O membranes and the desolvation effect of the ions is responsible for the selectivity of G-O membranes toward the penetration of different ions. These results help us better understand the ion transport process through G-O membranes, from which the possibility of modeling the ion transport behavior of cellular membrane using G-O can be discussed further. The selectivity toward different ions also makes G-O membrane a promising candidate in areas of membrane separations.

  7. Promoting alkali and alkaline-earth metals on MgO for enhancing CO2 capture by first-principles calculations.

    PubMed

    Kim, Kiwoong; Han, Jeong Woo; Lee, Kwang Soon; Lee, Won Bo

    2014-12-07

    Developing next-generation solid sorbents to improve the economy of pre- and post-combustion carbon capture processes has been challenging for many researchers. Magnesium oxide (MgO) is a promising sorbent because of its moderate sorption-desorption temperature and low heat of sorption. However, its low sorption capacity and thermal instability need to be improved. Various metal-promoted MgO sorbents have been experimentally developed to enhance the CO2 sorption capacities. Nevertheless, rigorous computational studies to screen an optimal metal promoter have been limited to date. We conducted first-principles calculations to select metal promoters of MgO sorbents. Five alkali (Li-, Na-, K-, Rb-, and Cs-) and 4 alkaline earth metals (Be-, Ca-, Sr-, and Ba-) were chosen as a set of promoters. Compared with the CO2 adsorption energy on pure MgO, the adsorption energy on the metal-promoted MgO sorbents is higher, except for the Na-promoter, which indicates that metal promotion on MgO is an efficient approach to enhance the sorption capacities. Based on the stabilized binding of promoters on the MgO surface and the regenerability of sorbents, Li, Ca, and Sr were identified as adequate promoters among the 9 metals on the basis of PW91/GGA augmented with DFT+D2. The adsorption energies of CO2 on metal-promoted MgO sorbents for Li, Ca, and Sr atoms are -1.13, -1.68, and -1.48 eV, respectively.

  8. Arsenic speciation in natural water samples by coprecipitation-hydride generation atomic absorption spectrometry combination.

    PubMed

    Tuzen, Mustafa; Citak, Demirhan; Mendil, Durali; Soylak, Mustafa

    2009-04-15

    A speciation procedure for As(III) and As(V) ions in environmental samples has been presented. As(V) was quantitatively recovered on aluminum hydroxide precipitate. After oxidation of As(III) by using dilute KMnO(4), the developed coprecipitation was applied to determination of total arsenic. Arsenic(III) was calculated as the difference between the total arsenic content and As(V) content. The determination of arsenic levels was performed by hydride generation atomic absorption spectrometry (HG-AAS). The analytical conditions for the quantitative recoveries of As(V) including pH, amount of aluminum as carrier element and sample volume, etc. on the presented coprecipitation system were investigated. The effects of some alkaline, earth alkaline, metal ions and also some anions were also examined. Preconcentration factor was calculated as 25. The detection limits (LOD) based on three times sigma of the blank (N: 21) for As(V) was 0.012 microg L(-1). The satisfactory results for the analysis of arsenic in NIST SRM 2711 Montana soil and LGC 6010 Hard drinking water certified reference materials for the validation of the method was obtained. The presented procedure was successfully applied to real samples including natural waters for arsenic speciation.

  9. Chemical composition of modern and fossil Hippopotamid teeth and implications for paleoenvironmental reconstructions and enamel formation - Part 2: Alkaline earth elements as tracers of watershed hydrochemistry and provenance

    NASA Astrophysics Data System (ADS)

    Brügmann, G.; Krause, J.; Brachert, T. C.; Stoll, B.; Weis, U.; Kullmer, O.; Ssemmanda, I.; Mertz, D. F.

    2012-03-01

    For reconstructing environmental change in terrestrial realms the geochemistry of fossil bioapatite in bones and teeth is among the most promising applications. This study demonstrates that alkaline earth elements in enamel of Hippopotamids, in particular Ba and Sr are tracers for water provenance and hydrochemistry. The studied specimens are molar teeth from Hippopotamids found in modern and fossil lacustrine settings of the Western Branch of the East African Rift system (Lake Kikorongo, Lake Albert, and Lake Malawi) and from modern fluvial environments of the Nile River. Concentrations in enamel vary by ca. two orders of magnitude for Ba (120-9336 μg g-1) as well as for Sr (9-2150 μg g-1). Concentration variations in enamel are partly induced during post-mortem alteration and during amelogenesis, but the major contribution originates from the variable water chemistry in the habitats of the Hippopotamids which is dominated by the lithologies and weathering processes in the watershed areas. Amelogenesis causes a distinct distribution of Ba and Sr in modern and fossil enamel, in that element concentrations increase along profiles from the outer rim towards the enamel-dentin junction by a factor of 1.3-1.5. These elements are well correlated with MgO and Na2O in single specimens, thus suggesting that their distribution is determined by a common, single process. Presuming that the shape of the tooth is established at the end of the secretion process and apatite composition is in equilibrium with the enamel fluid, the maturation process can be modeled by closed system Rayleigh crystallization. Enamel from many Hippopotamid specimens has Sr/Ca and Ba/Ca which are typical for herbivores, but the compositions extend well into the levels of plants and carnivores. Within enamel from single specimens these element ratios covary and provide a specific fingerprint of the Hippopotamid habitat. All specimens together, however, define subparallel trends with different Ba

  10. 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.

  11. 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.

  12. Materials engineering of metal hydrides

    SciTech Connect

    Gruen, D.M.; Mendelsohn, M.H.

    1981-01-01

    Intermetallic hydrides of the AB/sub 5/ type have enthalpies in the range valid for chemical heat pumps. A scheme for manufacturing hydrides with optimal properties for a chemical heat pump is described, using LaNi/sub 5-x/Al/sub x/ and ZrV/sub 2x/Cr/sub x as examples. The Laves-phase ternary hydrides appear to be good candidates for gettering hydrogen in the Tokamak Fusion Test Reactor. (DLC)

  13. Superstoichiometric hydride of zirconium

    SciTech Connect

    Kupryazhkin, A.Ya.; Shchepetkin, A.A.; Zabolotskaya, E.V.; Pletnev, R.N.; Alyamovskii, S.I.; Kitaev, G.A.

    1987-12-01

    Superstoichiometric hydrides of zirconium have been obtained all the way up to the composition ZrH/sub 2.4/ by additional hydrogenation of ZrH/sub 2/ as a result of redistribution of hydrogen atoms between t- and o-positions. In the preparation of the hydrides the authors used zirconium iodide with an impurity content no greater than 10/sup -2/ to 10/sup -2/ mole %; the hydrogen and helium used in this work had a minimum purity of 99.95%. The content of hydrogen in the specimens was determined by a volumetric method. The x-ray diffraction analysis was performed in a DRON-2.0 unit (CuK/sub ..cap alpha../ radiation). PMR spectra were recorded in a broad-line spectrometer in the temperature interval 150-450 K.

  14. Hydrogen Outgassing from Lithium Hydride

    SciTech Connect

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

    2006-04-20

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

  15. Chemical composition of modern and fossil hippopotamid teeth and implications for paleoenvironmental reconstructions and enamel formation - Part 2: Alkaline earth elements as tracers of watershed hydrochemistry and provenance

    NASA Astrophysics Data System (ADS)

    Brügmann, G.; Krause, J.; Brachert, T. C.; Stoll, B.; Weis, U.; Kullmer, O.; Ssemmanda, I.; Mertz, D. F.

    2012-11-01

    This study demonstrates that alkaline earth elements in enamel of hippopotamids, in particular Ba and Sr, are tracers for water provenance and hydrochemistry in terrestrial settings. The studied specimens are permanent premolar and molar teeth found in modern and fossil lacustrine sediments of the Western Branch of the East African Rift system (Lake Kikorongo, Lake Albert, and Lake Malawi) and from modern fluvial environments of the Nile River. Concentrations in enamel vary by two orders of magnitude for Ba (120-9336 μg g-1) as well as for Sr (9-2150 μg g-1). The variations are partially induced during post-mortem alteration and during amelogenesis, but the major contribution originates ultimately from the variable water chemistry in the habitats of the hippopotamids which is controlled by the lithologies and weathering processes in the watershed areas. Amelogenesis causes a distinct distribution of MgO, Ba and Sr in modern and fossil enamel, in that element concentrations increase along profiles from the outer rim towards the enamel-dentin junction by a factor of 1.3-1.9. These elements are well correlated in single specimens, thus suggesting that their distribution is determined by a common, single process, which can be described by closed system Rayleigh crystallization of bioapatite in vivo. Enamel from most hippopotamid specimens has Sr/Ca and Ba/Ca which are typical for herbivores. However, Ba/Sr ranges from 0.1 to 3 and varies on spatial and temporal scales. Thus, Sr concentrations and Ba/Sr in enamel differentiate between habitats having basaltic mantle rocks or Archean crustal rocks as the ultimate sources of Sr and Ba. This provenance signal is modulated by climate change. In Miocene to Pleistocene enamel from the Lake Albert region, Ba/Sr decreases systematically with time from 2 to 0.5. This trend can be correlated with changes in climate from humid to arid, in vegetation from C3 to C4 biomass as well as with increasing evaporation of the lake water

  16. 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

  17. Polar intermetallic compounds of the silicon and arsenic family elements and their ternary hydrides and fluorides

    SciTech Connect

    Leon-Escamilla, E.A.

    1996-10-17

    An investigation has been made on the effects of hydrogen and fluoride in the solid state chemistry of alkaline-earth and divalent rare-earth metal pnictide (Pn) and tetrelide (Tt) phases A{sub 5}(Pn,Tt,){sub 3}Z{sub x}, where A = Ca, Sr, Ba, Sm, Eu, Yb; Pn = As, Sb, Bi; Tt = Si, Ge, Sn, Pb and Z = H, F. Several trivalent rare-earth-metal pnictides, RE{sub 5}Pn{sub 3} (RE = Y, La, Gd, Tb, Dy, Ho, Er, Tm) and alkaline-earth-metal trielides, A{sub 5}Tr{sub 3}Z{sub x} (Tr = Ga, In, Tl) have been included in an effort to complete observed structural trends. Two main experimental techniques were followed throughout this work, (a) reactions in absence of hydrogen or under continuous high vacuum, and (b) reactions with binary metal hydrides, AH{sub x}, in closed containers. The results demonstrate that all the phases reported with the {beta}-Yb{sub 5}Sb{sub 3}-type structure in the A{sub 5}Pn{sub 3} systems are hydrogen-stabilized compounds. Reactions in absence of hydrogen lead to compounds with the Mn{sub 5}Si{sub 3}-type structure. The structure type {beta}-Yb{sub 5}Sb{sub 3} (= Ca{sub 5}SB{sub 3}F) was found to be characteristic of ternary systems and inaccurately associated with phases that form in the Y{sub 5}Bi{sub 3}-type. A new series of isomorphous Zintl compounds with the Ca{sub 16}Sb{sub 11}-type structure were prepared and studied as well. All the alkaline-earth-metal tetrelides, A{sub 5}Tt{sub 3}, that crystallize in the Cr{sub 5}B{sub 3}-type structure can be interstitially derivatized by hydrogen or fluoride. Binary and ternary compounds were characterized by Guinier powder patterns, single crystal X-ray and powder neutron diffraction techniques. In an effort to establish property-structure relationships, electrical resistivity and magnetic measurements were performed on selected systems, and the results were explained in terms of the Zintl concepts, aided by extended Hueckel band calculations.

  18. Hydrogenation using hydrides and acid

    DOEpatents

    Bullock, R. Morris

    1990-10-30

    A process for the non-catalytic hydrogenation of organic compounds, which contain at least one reducible functional group, which comprises reacting the organic compound, a hydride complex, preferably a transition metal hydride complex or an organosilane, and a strong acid in a liquid phase.

  19. Charge Compensation in RE3+ (RE = Eu, Gd) and M+ (M = Li, Na, K) Co-Doped Alkaline Earth Nanofluorides Obtained by Microwave Reaction with Reactive Ionic Liquids Leading to Improved Optical Properties

    SciTech Connect

    Lorbeer, C; Behrends, F; Cybinska, J; Eckert, H; Mudring, Anja -V

    2014-01-01

    Alkaline earth fluorides are extraordinarily promising host matrices for phosphor materials with regard to rare earth doping. In particular, quantum cutting materials, which might considerably enhance the efficiency of mercury-free fluorescent lamps or SC solar cells, are often based on rare earth containing crystalline fluorides such as NaGdF4, GdF3 or LaF3. Substituting most of the precious rare earth ions and simultaneously retaining the efficiency of the phosphor is a major goal. Alkaline earth fluoride nanoparticles doped with trivalent lanthanide ions (which are required for the quantum cutting phenomenon) were prepared via a microwave assisted method in ionic liquids. As doping trivalent ions into a host with divalent cations requires charge compensation, this effect was thoroughly studied by powder X-ray and electron diffraction, luminescence spectroscopy and 23Na, 139La and 19F solid state NMR spectroscopy. Monovalent alkali ions were codoped with the trivalent lanthanide ions to relieve stress and achieve a better crystallinity and higher quantum cutting abilities of the prepared material. 19F-magic angle spinning (MAS)-NMR-spectra, assisted by 19F{23Na} rotational echo double resonance (REDOR) studies, reveal distinct local fluoride environments, the populations of which are discussed in relation to spatial distribution and clustering models. In the co-doped samples, fluoride species having both Na+ and La3+ ions within their coordination sphere can be identified and quantified. This interplay of mono- and trivalent ions in the CaF2 lattice appears to be an efficient charge compensation mechanism that allows for improved performance characteristics of such co-doped phosphor materials.

  20. {sup 1}H and {sup 23}Na MAS NMR spectroscopy of cationic species in CO{sub 2} selective alkaline earth metal porous silicoaluminophosphates prepared via liquid and solid state ion exchange

    SciTech Connect

    Arevalo-Hidalgo, Ana G.; Dugar, Sneha; Fu, Riqiang; Hernandez-Maldonado, Arturo J.

    2012-07-15

    The location of extraframework cations in Sr{sup 2+} and Ba{sup 2+} ion-exchanged SAPO-34 was estimated by means of {sup 1}H and {sup 23}Na MAS NMR spectroscopy and spectral deconvolution. Incorporation of the alkaline earth metal cations onto the SAPO framework was achieved via liquid state ion exchange, coupled partial detemplation/solid-state ion exchange, and combination of both techniques. MAS NMR revealed that the level of ion exchange was limited by the presence of protons and sodium cations near hexagonal prisms (site SI), which are relatively difficult to exchange with the alkaline earth metal due to steric and charge repulsion criteria. In addition, the presence of ammonium cations in the supercages facilitated the exchange of otherwise tenacious hydrogen as corroborated by unit cell compositional data as well as enhanced CO{sub 2} adsorption at low partial pressures. The extraframework ammonium species were produced from partial detemplation of the structure-directing agent employed for the SAPO-34 synthesis, tetraethylammonium. - Graphical abstract: MAS NMR was used to elucidate the position the cationic species in alkaline earth metal exchanged silicoaluminophosphates. These species played a significant role during the ion exchange process and, therefore, the materials ultimate CO{sub 2} adsorption performance. Highlights: Black-Right-Pointing-Pointer Location of extraframework Sr{sup 2+} or Ba{sup 2+} cations was estimated by means of {sup 1}H and {sup 23}Na MAS NMR. Black-Right-Pointing-Pointer Level of Sr{sup 2+} or Ba{sup 2+} ion exchange was limited by the presence of protons and sodium cations. Black-Right-Pointing-Pointer Presence of ammonium cations in the supercages facilitated the exchange. Black-Right-Pointing-Pointer Sr{sup 2+} and Ba{sup 2+} ion exchanged SAPOs are outstanding CO{sub 2} adsorbents.

  1. Ni/metal hydride secondary element

    DOEpatents

    Bauerlein, Peter

    2005-04-19

    A Ni/metal hydride secondary element having a positive nickel hydroxide electrode, a negative electrode having a hydrogen storage alloy, and an alkaline electrolyte, the positive electrode, provided with a three-dimensional metallic conductive structure, also contains an aluminum compound which is soluble in the electrolyte, in addition to nickel hydroxide and cobalt oxide. The aluminum compound is aluminum hydroxide and/or aluminum oxide, and the mass of the aluminum compound which is present in the positive bulk material mixture is 0.1 to 2% by weight relative to the mass of the nickel hydroxide which is present. In combination with aluminum hydroxide or aluminum oxide, the positive electrode further contains lanthanoid oxidic compounds Y.sub.2 O.sub.3, La.sub.2 O.sub.3 and Ca(OH).sub.2, as well as mixtures of these compounds.

  2. 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.

  3. Thin-film metal hydrides.

    PubMed

    Remhof, Arndt; Borgschulte, Andreas

    2008-12-01

    The goal of the medieval alchemist, the chemical transformation of common metals into nobel metals, will forever be a dream. However, key characteristics of metals, such as their electronic band structure and, consequently, their electric, magnetic and optical properties, can be tailored by controlled hydrogen doping. Due to their morphology and well-defined geometry with flat, coplanar surfaces/interfaces, novel phenomena may be observed in thin films. Prominent examples are the eye-catching hydrogen switchable mirror effect, the visualization of solid-state diffusion and the formation of complex surface morphologies. Thin films do not suffer as much from embrittlement and/or decrepitation as bulk materials, allowing the study of cyclic absorption and desorption. Therefore, thin-metal hydride films are used as model systems to study metal-insulator transitions, for high throughput combinatorial research or they may be used as indicator layers to study hydrogen diffusion. They can be found in technological applications as hydrogen sensors, in electrochromic and thermochromic devices. In this review, we discuss the effect of hydrogen loading of thin niobium and yttrium films as archetypical examples of a transition metal and a rare earth metal, respectively. Our focus thereby lies on the hydrogen induced changes of the electronic structure and the morphology of the thin films, their optical properties, the visualization and the control of hydrogen diffusion and on the study of surface phenomena and catalysis.

  4. Stabilization of 3d Transition Metal Hydrido Complexes in SrH2Mg2[Co(I)H5], BaH2Mg5[Co(-I)H4]2, and RbH2Mg5[Co(-I)H4 Ni(0)H4] via Easily Polarizable Hydride Ligands.

    PubMed

    Fahlquist, Henrik; Moser, David; Noréus, Dag; Refson, Keith; Parker, Stewart F

    2016-04-04

    A combined study using neutron diffraction, inelastic neutron scattering, and first-principles calculations describe cobalt with a very low formal oxidation state of (-I) in a slightly distorted tetrahedral Co(-I)H4-complex in BaH2Mg5[Co(-I)H4]2 and in the structurally related RbH2Mg5[Co(-I)H4 Ni(0)H4]. This indicates that the electron "back donating" effect via the polarizable hydride ions to the counterions in the solid state hydrides, can be compared to more conventional "back bonding" able to reduce the oxidation state down to -I. The hydrides were synthesized by hot sintering of transition metal powders with corresponding binary alkali- and alkaline earth hydrides. In the similarly synthesized SrH2Mg2[Co(I)H5], cobalt is formally + I-valent, showing a high sensitivity to differences in the counterion framework, which can also influence electrical properties.

  5. Complex Hydride Compounds with Enhanced Hydrogen Storage Capacity

    SciTech Connect

    Mosher, Daniel A.; Opalka, Susanne M.; Tang, Xia; Laube, Bruce L.; Brown, Ronald J.; Vanderspurt, Thomas H.; Arsenault, Sarah; Wu, Robert; Strickler, Jamie; Anton, Donald L.; Zidan, Ragaiy; Berseth, Polly

    2008-02-18

    between alkaline metal hydrides (AmH), Alkaline earth metal hydrides (AeH2), alane (AlH3), transition metal (Tm) hydrides (TmHz, where z=1-3) and molecular hydrogen (H2). The effort started first with variations of known alanates and subsequently extended the search to unknown compounds. In this stage, the FPM techniques were developed and validated on known alanate materials such as NaAlH4 and Na2LiAlH6. The coupled predictive methodologies were used to survey over 200 proposed phases in six quaternary spaces, formed from various combinations of Na, Li Mg and/or Ti with Al and H. A wide range of alanate compounds was examined using SSP having additions of Ti, Cr, Co, Ni and Fe. A number of compositions and reaction paths were identified having H weight fractions up to 5.6 wt %, but none meeting the 7.5 wt%H reversible goal. Similarly, MSP of alanates produced a number of interesting compounds and general conclusions regarding reaction behavior of mixtures during processing, but no alanate based candidates meeting the 7.5 wt% goal. A novel alanate, LiMg(AlH4)3, was synthesized using SBP that demonstrated a 7.0 wt% capacity with a desorption temperature of 150°C. The deuteride form was synthesized and characterized by the Institute for Energy (IFE) in Norway to determine its crystalline structure for related FPM studies. However, the reaction exhibited exothermicity and therefore was not reversible under acceptable hydrogen gas pressures for on-board recharging. After the extensive studies of alanates, the material class of emphasis was shifted to borohydrides. Through SBP, several ligand-stabilized Mg(BH4)2 complexes were synthesized. The Mg(BH4)2*2NH3 complex was found to change behavior with slightly different synthesis conditions and/or aging. One of the two mechanisms was an amine-borane (NH3BH3) like dissociation reaction which released up to 16 wt %H and more conservatively 9 wt%H when not including H2 released from the NH3. From FPM, the stability of the Mg(BH4

  6. First-principles study of fission product (Xe, Cs, Sr) incorporation and segregation in alkaline earth metal oxides, HfO2, and MgO-HfO2 interface

    SciTech Connect

    Liu, Xiang-yang; Uberuaga, Blas P; Sickafus, Kurt E

    2008-01-01

    In order to close the nuclear fuel cycle, advanced concepts for separating out fission products are necessary. One approach is to use a dispersion fuel form in which a fissile core is surrounded by an inert matrix that captures and immobilizes the fission products from the core. If this inert matrix can be easily separated from the fuel, via e.g. solution chemistry, the fission products can be separated from the fissile material. We examine a surrogate dispersion fuel composition, in which hafnia (HfO{sub 2}) is a surrogate for the fissile core and alkaline earth metal oxides are used as the inert matrix. The questions of fission product incorporation in these oxides and possible segregation behavior at interfaces are considered. Density functional theory based calculations for fission product elements (Xe, Sr, and Cs) in these oxides are carried out. We find smaller incorporation energy in hafnia than in MgO for Cs and Sr, and Xe if variation of charge state is allowed. We also find that this trend is reversed or reduced for alkaline earth metal oxides with large cation sizes. Model interfacial calculations show a strong tendency of segregation from bulk MgO to MgO-HfO{sub 2} interfaces.

  7. Influences of alkaline earth metal substitution on the crystal structure and physical properties of magnetic RuSr1.9A0.1GdCu2O8 (A = Ca, Sr, and Ba) superconductors.

    PubMed

    Hur, Su Gil; Park, Dae Hoon; Hwang, Seong-Ju; Kim, Seung Joo; Lee, J H; Lee, Sang Young

    2005-11-24

    We have investigated the effect of alkaline earth metal substitution on the crystal structure and physical properties of magnetic superconductors RuSr(1.9)A(0.1)GdCu(2)O(8) (A = Ca, Sr, and Ba) in order to probe an interaction between the magnetic coupling of the RuO(2) layer and the superconductivity of the CuO(2) layer. X-ray diffraction and X-ray absorption spectroscopic analyses demonstrate that the isovalent substitution of Sr ions with Ca or Ba ions makes it possible to tune the interlayer distance between the CuO(2) and the RuO(2) layers. From the measurements of electrical resistance and magnetic susceptibility, it was found that, in contrast to negligible change of magnetization, both of the alkaline earth metal substitutions lead to a notable depression of zero-resistance temperature T(c) (DeltaT(c) approximately 17-19 K). On the basis of the absence of a systematic correlation between the T(c) and the interlayer distance/magnetization, we have concluded that the internal magnetic field of the RuO(2) layer has insignificant influence on the superconducting property of the CuO(2) layer in the ruthenocuprate.

  8. Alkaline quinone flow battery.

    PubMed

    Lin, Kaixiang; Chen, Qing; Gerhardt, Michael R; Tong, Liuchuan; Kim, Sang Bok; Eisenach, Louise; Valle, Alvaro W; Hardee, David; Gordon, Roy G; Aziz, Michael J; Marshak, Michael P

    2015-09-25

    Storage of photovoltaic and wind electricity in batteries could solve the mismatch problem between the intermittent supply of these renewable resources and variable demand. Flow batteries permit more economical long-duration discharge than solid-electrode batteries by using liquid electrolytes stored outside of the battery. We report an alkaline flow battery based on redox-active organic molecules that are composed entirely of Earth-abundant elements and are nontoxic, nonflammable, and safe for use in residential and commercial environments. The battery operates efficiently with high power density near room temperature. These results demonstrate the stability and performance of redox-active organic molecules in alkaline flow batteries, potentially enabling cost-effective stationary storage of renewable energy.

  9. Complex Hydrides for Hydrogen Storage

    SciTech Connect

    Slattery, Darlene; Hampton, Michael

    2003-03-10

    This report describes research into the use of complex hydrides for hydrogen storage. The synthesis of a number of alanates, (AIH4) compounds, was investigated. Both wet chemical and mechano-chemical methods were studied.

  10. 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.

  11. A set of alkali and alkaline-earth coordination polymers based on the ligand 2-(1H-benzotriazol-1-yl) acetic acid: Effects the radius of metal ions on structures and properties

    SciTech Connect

    Wang, Jin-Hua; Tang, Gui-Mei; Qin, Ting-Xiao; Yan, Shi-Chen; Wang, Yong-Tao; Cui, Yue-Zhi; Weng Ng, Seik

    2014-11-15

    Four new metal coordination complexes, namely, [Na(BTA)]{sub n} (1), [K{sub 2}(BTA){sub 2}(μ{sub 2}-H{sub 2}O)]{sub n} (2), and [M(BTA){sub 2}(H{sub 2}O){sub 2}]{sub n} (M=Ca(II) and Sr(II) for 3 and 4, respectively) [BTA=2-(1H-benzotriazol-1-yl) acetic anion], have been obtained under hydrothermal condition, by reacting the different alkali and alkaline-earth metal hydroxides with HBTA. Complexes 1–4 were structurally characterized by X-ray single-crystal diffraction, EA, IR, PXRD, and thermogravimetry analysis (TGA). These complexes display low-dimensional features displaying various two-dimensional (2D) and one-dimensional (1D) coordination motifs. Complex 1 displays a 2D layer with the thickness of 1.5 nm and possesses a topologic structure of a 11 nodal net with Schläfli symbol of (3{sup 18}). Complex 2 also shows a thick 2D sheet and its topologic structure is a 9 nodes with Schläfli symbol of (3{sup 11}×4{sup 2}). Complexes 3 and 4 possess a 1D linear chain and further stack via hydrogen bonding interactions to generate a three-dimensional supramolecular architecture. These results suggest that both the coordination preferences of the metal ions and the versatile nature of this flexible ligand play a critical role in the final structures. The luminescent spectra show strong emission intensities in complexes 1–4, which display violet photoluminescence. Additionally, ferroelectric, dielectric and nonlinear optic (NLO) second-harmonic generation (SHG) properties of 2 are discussed in detail. - Graphical abstract: A set of alkali and alkaline-earth metal coordination polymers were hydrothermally synthesized by 2-(1H-benzotriazol-1-yl)acetic acid, displaying interesting topologic motifs from two-dimension to one-dimension and specific physical properties. - Highlights: • Alkali and alkaline-earth metal coordination polymers have been obtained. • The ligand 2-(1H-benzotriazol-1-yl)acetic acid has been adopted. • The two-dimensional and one

  12. Complex and liquid hydrides for energy storage

    NASA Astrophysics Data System (ADS)

    Callini, Elsa; Atakli, Zuleyha Özlem Kocabas; Hauback, Bjørn C.; Orimo, Shin-ichi; Jensen, Craig; Dornheim, Martin; Grant, David; Cho, Young Whan; Chen, Ping; Hjörvarsson, Bjørgvin; de Jongh, Petra; Weidenthaler, Claudia; Baricco, Marcello; Paskevicius, Mark; Jensen, Torben R.; Bowden, Mark E.; Autrey, Thomas S.; Züttel, Andreas

    2016-04-01

    The research on complex hydrides for hydrogen storage was initiated by the discovery of Ti as a hydrogen sorption catalyst in NaAlH4 by Boris Bogdanovic in 1996. A large number of new complex hydride materials in various forms and combinations have been synthesized and characterized, and the knowledge regarding the properties of complex hydrides and the synthesis methods has grown enormously since then. A significant portion of the research groups active in the field of complex hydrides is collaborators in the International Energy Agreement Task 32. This paper reports about the important issues in the field of complex hydride research, i.e. the synthesis of borohydrides, the thermodynamics of complex hydrides, the effects of size and confinement, the hydrogen sorption mechanism and the complex hydride composites as well as the properties of liquid complex hydrides. This paper is the result of the collaboration of several groups and is an excellent summary of the recent achievements.

  13. Complex and liquid hydrides for energy storage

    SciTech Connect

    Callini, Elsa; Atakli, Zuleyha Özlem Kocabas; Hauback, Bjørn C.; Orimo, Shin-ichi; Jensen, Craig; Dornheim, Martin; Grant, David; Cho, Young Whan; Chen, Ping; Hjörvarsson, Bjørgvin; de Jongh, Petra; Weidenthaler, Claudia; Baricco, Marcello; Paskevicius, Mark; Jensen, Torben R.; Bowden, Mark E.; Autrey, Thomas S.; Züttel, Andreas

    2016-03-10

    The research on complex hydrides for hydrogen storage was imitated by the discovery of Ti as a hydrogen sorption catalyst in NaAlH4 by Boris Bogdanovic in 1996. A large number of new complex hydride materials in various forms and combinations have been synthesized and characterized and the knowledge on the properties of complex hydrides and the synthesis methods has grown enormously since then. A significant part of the research groups active in the field of complex hydrides are collaborators in the IEA task 32. This paper reports about the important issues in the field of the complex hydride research, i.e. the synthesis of borohydrides, the thermodynamics of complex hydrides and their thermodynamic properties, the effects of size and confinement, the hydrogen sorption mechanism and the complex hydride composites as well as the properties of liquid complex hydrides. This paper is the result of the collaboration of several groups and excellent summary of the recent achievements.

  14. Effect of alkaline earth oxides on the physical and spectroscopic properties of Dy3+- doped Li2O-B2O3 glasses for white emitting material application

    NASA Astrophysics Data System (ADS)

    Shamshad, L.; Rooh, G.; Kirdsiri, K.; Srisittipokakun, N.; Damdee, B.; Kim, H. J.; Kaewkhao, J.

    2017-02-01

    Li2O-MO-B2O3:0.5Dy2O3 glasses mixed with four different alkaline earth modifier oxides MgO, CaO, SrO and BaO were synthesized by melt quench technique. Their physical properties like density, molar volume and refractive index were measured at room temperature and the effect of alkaline earth modifier oxides were studied. Also, optical absorption and photoluminescence spectra of these glasses have been acquired at room temperature. The Judd-Ofelt theory was effectively used to characterize these spectra and spectral intensities (ƒcal), Judd-Ofelt intensity parameters (Ω2, Ω4 and Ω6) and certain radiative properties have been determined. Radiative life-times (τR), branching ratios (βcal), and emission cross-sections (σp) and optical gain parameters (σp × τR) were calculated from the Judd-Ofelt intensity parameters and the variation in these parameters with the variation of glass matrix are discussed. Yellow/Blue (Y/B) ratio and chromacity color coordinates (x,y) are calculated from the emission spectra which indicates the white light generation from all the investigated samples. The correlated color temperature (CCT) for the studied glasses is found to be 4418 K. The fluorescence decay time (τexp) of the 4F9/2 level of Dy3+ has been measured from the decay profiles and compared with calculated lifetimes (τcal). Among all the studied glass matrices, the glass containing BaO exhibits high value of branching ratio, large emission cross-section and high optical gain parameter for 6F9/2 → 6H13 at 575 nm. The results indicates the suitability of all the studied glasses for laser action and white light generation.

  15. A new route to metal hydrides

    SciTech Connect

    Murphy, D.W.; Zahurak, S.M.; Vyas, B.; Thomas, M.; Badding, M.E.; Fang, W.C. )

    1993-06-01

    Aqueous borohydride is shown to be an effective reagent for hydriding metals and intermetallics. It is the hydriding equivalent of 20-30 atm of H[sub 2]. The reaction is a convenient way to screen materials for hydride formation and possible utility in applications such as nickel-metal hydride batteries. The reaction is also a convenient alternative to decrepitation for the production of free flowing powders. 16 refs., 1 fig., 1 tab.

  16. Gas-phase acidities of binary hydrides.

    NASA Technical Reports Server (NTRS)

    Brauman, J. I.; Eyler, J. R.; Blair, L. K.; White, M. J.; Comisarow, M. B.; Smyth, K. C.

    1971-01-01

    The preferred direction of proton transfer in a reaction between a hydride molecule and a hydride ion was studied in order to determine the relative acidities of some binary hydrides. Sufficient data are presented to make clear the periodic trends in acidities and the underlying trends in other fundamental thermochemical quantities which influence acidity. The bond dissociation energies and electron affinities of the hydrides considered are listed in a table.

  17. Photochemistry of Transition Metal Hydrides.

    PubMed

    Perutz, Robin N; Procacci, Barbara

    2016-08-10

    Photochemical reactivity associated with metal-hydrogen bonds is widespread among metal hydride complexes and has played a critical part in opening up C-H bond activation. It has been exploited to design different types of photocatalytic reactions and to obtain NMR spectra of dilute solutions with a single pulse of an NMR spectrometer. Because photolysis can be performed on fast time scales and at low temperature, metal-hydride photochemistry has enabled determination of the molecular structure and rates of reaction of highly reactive intermediates. We identify five characteristic photoprocesses of metal monohydride complexes associated with the M-H bond, of which the most widespread are M-H homolysis and R-H reductive elimination. For metal dihydride complexes, the dominant photoprocess is reductive elimination of H2. Dihydrogen complexes typically lose H2 photochemically. The majority of photochemical reactions are likely to be dissociative, but hydride complexes may be designed with equilibrated excited states that undergo different photochemical reactions, including proton transfer or hydride transfer. The photochemical mechanisms of a few reactions have been analyzed by computational methods, including quantum dynamics. A section on specialist methods (time-resolved spectroscopy, matrix isolation, NMR, and computational methods) and a survey of transition metal hydride photochemistry organized by transition metal group complete the Review.

  18. 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.

  19. 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.

  20. 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.

  1. Characteristics and Applications of Metal Hydrides

    NASA Technical Reports Server (NTRS)

    Egan, G. J.; Lynch, F. E.

    1987-01-01

    Report discusses engineering principles of uses of metal hydrides in spacecraft. Metal hydrides absorb, store, pump, compress, and expand hydrogen gas. Additionally, they release or absorb sizeable amounts of heat as they form and decompose - property adapted for thermal-energy management or for propulsion. Describes efforts to: Identify heat sources and sinks suitable for driving metal hydride thermal cycles in spacecraft; develop concepts for hydride subsystems employing available heating and cooling methods; and produce data base on estimated sizes, masses, and performances of hydride devices for spacecraft.

  2. Characterization of hydrides and delayed hydride cracking in zirconium alloys

    NASA Astrophysics Data System (ADS)

    Fang, Qiang

    This thesis tries to fill some of the missing gaps in the study of zirconium hydrides with state-of-art experiments, cutting edge tomographical technique, and a novel numerical algorithm. A new hydriding procedure is proposed. The new anode material and solution combination overcomes many drawbacks of the AECLRTM hydriding method and leads to superior hydriding result compared to the AECL RTM hydriding procedure. The DHC crack growth velocity of as-received Excel alloy and Zr-2.5Nb alloy together with several different heat treated Excel alloy samples are measured. While it already known that the DHC crack growth velocity increases with the increase of base metal strength, the finding that the transverse plane is the weaker plane for fatigue crack growth despite having higher resistance to DHC crack growth was unexpected. The morphologies of hydrides in a coarse grained Zircally-2 sample have been studied using synchrotron x-rays at ESRF with a new technique called Diffraction Contrast Tomography that uses simultaneous collection of tomographic data and diffraction data to determine the crystallographic orientation of crystallites (grains) in 3D. It has been previously limited to light metals such as Al or Mg (due to the use of low energy x-rays). Here we show the first DCT measurements using high energy x-rays (60 keV), allowing measurements in zirconium. A new algorithm of a computationally effcient way to characterize distributions of hydrides - in particular their orientation and/or connectivity - has been proposed. It is a modification of the standard Hough transform, which is an extension of the Hough transform widely used in the line detection of EBSD patterns. Finally, a basic model of hydrogen migration is built using ABAQUS RTM, which is a mature finite element package with tested modeling modules of a variety of physical laws. The coupling of hydrogen diffusion, lattice expansion, matrix deformation and phase transformation is investigated under

  3. Cheaper Hydride-Forming Cathodes

    NASA Technical Reports Server (NTRS)

    Jones, Jack A.; Blue, Gary

    1990-01-01

    Hydride-forming cathodes for electrochemical experiments made of materials or combinations of materials cheaper and more abundant than pure palladium, according to proposal. Concept prompted by needs of experimenters in now-discredited concept of electrochemical nuclear fusion, cathodes useful in other electrochemical applications involving generation or storage of hydrogen, deuterium, or tritium.

  4. Properties of nanoscale metal hydrides.

    PubMed

    Fichtner, Maximilian

    2009-05-20

    Nanoscale hydride particles may exhibit chemical stabilities which differ from those of a macroscopic system. The stabilities are mainly influenced by a surface energy term which contains size-dependent values of the surface tension, the molar volume and an additional term which takes into account a potential reduction of the excess surface energy. Thus, the equilibrium of a nanoparticular hydride system may be shifted to the hydrogenated or to the dehydrogenated side, depending on the size and on the prefix of the surface energy term of the hydrogenated and dehydrogenated material. Additional complexity appears when solid-state reactions of complex hydrides are considered and phase segregation has to be taken into account. In such a case the reversibility of complex hydrides may be reduced if the nanoparticles are free standing on a surface. However, it may be enhanced if the system is enclosed by a nanoscale void which prevents the reaction partners on the dehydrogenated side from diffusing away from each other. Moreover, the generally enhanced diffusivity in nanocrystalline systems may lower the kinetic barriers for the material's transformation and, thus, facilitate hydrogen absorption and desorption.

  5. Microstructure of surface cerium hydride growth sites

    SciTech Connect

    Brierley, Martin; Knowles, John; Montgomery, Neil; Preuss, Michael

    2014-05-15

    Samples of cerium were exposed to hydrogen under controlled conditions causing cerium hydride sites to nucleate and grow on the surface. The hydriding rate was measured in situ, and the hydrides were characterised using secondary ion mass spectrometry, scanning electron microscopy, and optical microscopy. The results show that the hydriding rate proceeded more quickly than earlier studies. Characterisation confirmed that the hydrogen is confined to the sites. The morphology of the hydrides was confirmed to be oblate, and stressed material was observed surrounding the hydride, in a number of cases lathlike features were observed surrounding the hydride sites laterally with cracking in the surface oxide above them. It is proposed that during growth the increased lattice parameter of the CeH{sub 2} induces a lateral compressive stress around the hydride, which relieves by the ca. 16% volume collapse of the γ-Ce to α-Ce pressure induced phase transition. Cracking of the surface oxide above the laths reduces the diffusion barrier to hydrogen reaching the metal/oxide interface surrounding the hydride site and contributes to the anisotropic growth of the hydrides.

  6. Vapor-liquid partitioning of alkaline earth and transition metals in NaCl-dominated hydrothermal fluids: An experimental study from 360 to 465 °C, near-critical to halite saturated conditions

    NASA Astrophysics Data System (ADS)

    Pester, Nicholas J.; Ding, Kang; Seyfried, William E.

    2015-11-01

    Multi-phase fluid flow is a common occurrence in magmatic hydrothermal systems; and extensive modeling efforts using currently established P-V-T-x properties of the NaCl-H2O system are impending. We have therefore performed hydrothermal flow experiments (360-465 °C) to observe vapor-liquid partitioning of alkaline earth and first row transition metals in NaCl-dominated source solutions. The data allow extraction of partition coefficients related to the intrinsic changes in both chlorinity and density along the two-phase solvus. The coefficients yield an overall decrease in vapor affinity in the order Cu(I) > Na > Fe(II) > Zn > Ni(II) ⩾ Mg ⩾ Mn(II) > Co(II) > Ca > Sr > Ba, distinguished with 95% confidence for vapor densities greater than ∼0.2 g/cm3. The alkaline earth metals are limited to purely electrostatic interactions with Cl ligands, resulting in an excellent linear correlation (R2 > 0.99) between their partition coefficients and respective ionic radii. Though broadly consistent with this relationship, relative behavior of the transition metals is not well resolved, being likely obscured by complex bonding processes and the potential participation of Na in the formation of tetra-chloro species. At lower densities (at/near halite saturation) partitioning behavior of all metals becomes highly non-linear, where M/Cl ratios in the vapor begin to increase despite continued decreases in chlorinity and density. We refer to this phenomenon as "volatility", which is broadly associated with substantial increases in the HCl/NaCl ratio (eventually to >1) due to hydrolysis of NaCl. Some transition metals (e.g., Fe, Zn) exhibit volatility prior to halite stability, suggesting a potential shift in vapor speciation relative to nearer critical regions of the vapor-liquid solvus. The chemistry of deep-sea hydrothermal fluids appears affected by this process during magmatic events, however, our results do not support suggestions of subseafloor halite precipitation

  7. Kinetic study of the α-tocopherol-regeneration reaction of ubiquinol-10 in methanol and acetonitrile solutions: notable effect of the alkali and alkaline earth metal salts on the reaction rates.

    PubMed

    Mukai, Kazuo; Oi, Masanori; Ouchi, Aya; Nagaoka, Shin-ichi

    2012-03-01

    A kinetic study of regeneration reaction of α-tocopherol (α-TocH) by ubiquinol-10 has been performed in the presence of four kinds of alkali and alkaline earth metal salts (LiClO(4), NaClO(4), NaI, and Mg(ClO(4))(2)) in methanol and acetonitrile solutions, using double-mixing stopped-flow spectrophotometry. The second-order rate constants (k(r)'s) for the reaction of α-tocopheroxyl (α-Toc•) radical with ubiquinol-10 increased and decreased notably with increasing concentrations of metal salts in methanol and acetonitrile, respectively. The k(r) values increased in the order of no metal salt < NaClO(4) ~ NaI < LiClO(4) < Mg(ClO(4))(2) at the same concentration of metal salts in methanol. On the other hand, in acetonitrile, the k(r) values decreased in the order of no metal salt > NaClO(4) ~ NaI > LiClO(4) > Mg(ClO(4))(2) at the same concentration of metal salts. The metal salts having a smaller ionic radius of cation and a larger charge of cation gave a larger k(r) value in methanol, and a smaller k(r) value in acetonitrile. The effect of anion was almost negligible in both the solvents. Notable effects of metal cations on the UV-vis absorption spectrum of α-Toc• radical were observed in aprotic acetonitrile solution, suggesting complex formation between α-Toc• and metal cations. On the other hand, effects of metal cations were negligible in protic methanol, suggesting that the complex formation between α-Toc• and metal cations is hindered by the hydrogen bond between α-Toc• and methanol molecules. The difference between the reaction mechanisms in methanol and acetonitrile solutions was discussed on the basis of the results obtained. High concentrations of alkali and alkaline earth metal salts coexist with α-TocH and ubiquinol-10 in plasma, blood, and many tissues, suggesting the contribution of the metal salts to the above regeneration reaction in biological systems.

  8. Synthesis, crystal and band structures, and optical properties of a new lanthanide-alkaline earth tellurium(IV) oxide: La{sub 2}Ba(Te{sub 3}O{sub 8})(TeO{sub 3}){sub 2}

    SciTech Connect

    Jiang Hailong; Kong Fang; Mao Jianggao

    2007-05-15

    A new quaternary lanthanide alkaline-earth tellurium(IV) oxide, La{sub 2}Ba(Te{sub 3}O{sub 8})(TeO{sub 3}){sub 2}, has been prepared by the solid-state reaction and structurally characterized. The compound crystallizes in monoclinic space group C2/c with a=19.119(3), b=5.9923(5), c=13.2970(19) A, {beta}=107.646(8){sup o}, V=1451.7(3) A{sup 3} and Z=4. La{sub 2}Ba(Te{sub 3}O{sub 8})(TeO{sub 3}){sub 2} features a 3D network structure in which the cationic [La{sub 2}Ba(TeO{sub 3}){sub 2}]{sup 4+} layers are cross-linked by Te{sub 3}O{sub 8} {sup 4-} anions. Both band structure calculation by the DFT method and optical diffuse reflectance spectrum measurements indicate that La{sub 2}Ba(Te{sub 3}O{sub 8})(TeO{sub 3}){sub 2} is a wide band-gap semiconductor. - Graphical abstract: A new quaternary lanthanide alkaline-earth tellurium(IV) oxide, La{sub 2}Ba(Te{sub 3}O{sub 8})(TeO{sub 3}){sub 2}, has been prepared by the solid-state reaction and structurally characterized. The structure of La{sub 2}Ba(Te{sub 3}O{sub 8})(TeO{sub 3}){sub 2} is 3D network in which the cationic [La{sub 2}Ba(TeO{sub 3}){sub 2}]{sup 4+} layers are cross-linked by Te{sub 3}O{sub 8} {sup 4-} anions. Both band structure calculation by the DFT method and optical diffuse reflectance spectrum measurements indicate that La{sub 2}Ba(Te{sub 3}O{sub 8})(TeO{sub 3}){sub 2} is a wide band-gap semiconductor.

  9. The renaissance of hydrides as energy materials

    NASA Astrophysics Data System (ADS)

    Mohtadi, Rana; Orimo, Shin-Ichi

    2016-12-01

    Materials based on hydrides have been the linchpin in the development of several practical energy storage technologies, of which the most prominent example is nickel-metal hydride batteries. Motivated by the need to meet the future's energy demand, the past decade has witnessed substantial advancements in the research and development of hydrides as media for hydrogen energy storage. More recently, new and rapidly evolving discoveries have positioned hydrides as highly promising materials for future electrochemical energy storage, such as electrolytes for mono- and divalent batteries, and anodes for lithium-ion batteries. In addition, the potential of hydrides in efficient power transmission has been recently revealed. In this Review, we highlight key advances and illustrate how the versatility of hydrides has not only yielded a meaningful past, but also ensures a very bright future.

  10. Rechargeable metal hydrides for spacecraft application

    NASA Astrophysics Data System (ADS)

    Perry, J. L.

    1988-09-01

    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.

  11. 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.

  12. Eu(2+)-Activated Alkaline-Earth Halophosphates, M5(PO4)3X:Eu(2+) (M = Ca, Sr, Ba; X = F, Cl, Br) for NUV-LEDs: Site-Selective Crystal Field Effect.

    PubMed

    Kim, Donghyeon; Kim, Sung-Chul; Bae, Jong-Seong; Kim, Sungyun; Kim, Seung-Joo; Park, Jung-Chul

    2016-09-06

    Eu(2+)-activated M5(PO4)3X (M = Ca, Sr, Ba; X = F, Cl, Br) compounds providing different alkaline-earth metal and halide ions were successfully synthesized and characterized. The emission peak maxima of the M5(PO4)3Cl:Eu(2+) (M = Ca, Sr, Ba) compounds were blue-shifted from Ca to Ba (454 nm for Ca, 444 nm for Sr, and 434 nm for Ba), and those of the Sr5(PO4)3X:Eu(2+) (X = F, Cl, Br) compounds were red-shifted along the series of halides, F → Cl → Br (437 nm for F, 444 nm for Cl, and 448 nm for Br). The site selectivity and occupancy of the activator ions (Eu(2+)) in the M5(PO4)3X:Eu(2+) (M = Ca, Sr, Ba; X = F, Cl, Br) crystal lattices were estimated based on theoretical calculation of the 5d → 4f transition energies of Eu(2+) using LCAO. In combination with the photoluminescence measurements and theoretical calculation, it was elucidated that the Eu(2+) ions preferably enter the fully oxygen-coordinated sites in the M5(PO4)3X:Eu(2+) (M = Ca, Sr, Ba; X = F, Cl, Br) compounds. This trend can be well explained by "Pauling's rules". These compounds may provide a platform for modeling a new phosphor and application in the solid-state lighting field.

  13. Hydrothermal synthesis and crystal structure of two new hydrated alkaline earth metal borates Sr3B6O11(OH)2 and Ba3B6O11(OH)2.

    PubMed

    Heyward, Carla; McMillen, Colin; Kolis, Joseph

    2012-04-02

    Two new hydrated borates Sr(3)B(6)O(11)(OH)(2) (1) and Ba(3)B(6)O(11)(OH)(2) (2) were hydrothermally synthesized. Their structures were determined by single-crystal X-ray diffraction and further characterized by IR, powder XRD, and DSC/TGA. Compound 1 crystallizes in the triclinic space group P-1 with unit cell parameters of a = 6.6275(13) Å, b = 6.6706(13) Å, c = 11.393(2) Å, α = 91.06(3)°, β = 94.50(3)°, and γ = 93.12(3)°, while compound 2 crystallizes in the noncentrosymmetric monoclinic space group Pc with a = 6.958(14) Å, b = 7.024(14) Å, c = 11.346(2) Å, and β = 90.10(3)°. In spite of the differences in symmetry and packing of the borate chains, both structures consist of the same fundamental building block (FBB) of a [B(6)O(11)(OH)(2)](-6) unit and three unique alkaline earth metal atoms.

  14. Spin-Spin Interactions in the Oxides A(3)M'MO(6) (M = Rh, Ir; A = Ca, Sr; M' = Alkaline Earth, Zn, Cd, Na) of the K(4)CdCl(6) Structure Type Examined by Electronic Structure Calculations.

    PubMed

    Lee, K.-S.; Koo, H.-J.; Whangbo, M.-H.

    1999-05-03

    The oxides A(3)M'MO(6) (M = Rh, Ir; A = Ca, Sr; M' = alkaline earth, Zn, Cd) of the K(4)CdCl(6) structure type consist of isolated (MO(6))(8)(-) octahedral anions and exhibit an antiferromagnetic ordering at low temperatures. The spin-spin interactions in these oxides, Ca(3)NaMO(6) (M = Ir, Ru), and Sr(3)NaRuO(6) were examined by calculating how strongly the t(2g)-block levels of adjacent (MO(6))((6+)(n)()())(-) (n = 1, 2) anions interact in the presence and absence of the intervening cations A(2+) and M' (n)()(+) (n = 1, 2). Our calculations show that the spin-spin interactions in these oxides are three-dimensional, and the superexchange interactions occur mainly through the short intrachain and interchain M-O.O-M linkages. When the M(n)()(+) cation is very small compared with the A(2+) cation, the intrachain interaction is substantially stronger than the interchain interaction. The opposite is found when the sizes of the M(n)()(+) and A(2+) cations become similar.

  15. Binding to Redox-Inactive Alkali and Alkaline Earth Metal Ions Strongly Deactivates the C-H Bonds of Tertiary Amides toward Hydrogen Atom Transfer to Reactive Oxygen Centered Radicals.

    PubMed

    Salamone, Michela; Carboni, Giulia; Mangiacapra, Livia; Bietti, Massimo

    2015-09-18

    The effect of alkali and alkaline earth metal ions on the reactions of the cumyloxyl radical (CumO(•)) with N,N-dimethylformamide (DMF) and N,N-dimethylacetamide (DMA) was studied by laser flash photolysis. In acetonitrile, a >2 order of magnitude decrease in the rate constant for hydrogen atom transfer (HAT) from the C-H bonds of these substrates (kH) was measured after addition of Li(+). This behavior was explained in terms of a strong interaction between Li(+) and the oxygen atom of both DMF and DMA that increases the extent of positive charge on the amide, leading to C-H bond deactivation toward HAT to the electrophilic radical CumO(•). Similar effects were observed after addition of Ca(2+), which was shown to strongly bind up to four equivalents of the amide substrates. With Mg(2+), weak C-H deactivation was observed for the first two substrate equivalents followed by stronger deactivation for two additional equivalents. No C-H deactivation was observed in DMSO after addition of Li(+) and Mg(2+). These results point toward the important role played by metal ion Lewis acidity and solvent Lewis basicity, indicating that C-H deactivation can be modulated by varying the nature of the metal cation and solvent and allowing for careful control over the HAT reactivity of amide substrates.

  16. Effect of high-energy electron irradiation in an electron microscope column on fluorides of alkaline earth elements (CaF2, SrF2, and BaF2)

    NASA Astrophysics Data System (ADS)

    Nikolaichik, V. I.; Sobolev, B. P.; Zaporozhets, M. A.; Avilov, A. S.

    2012-03-01

    The effect of high-energy (150 eV) electron irradiation in an electron microscope column on crystals of fluorides of alkaline earth elements CaF2, SrF2, and BaF2 is studied. During structural investigations by electron diffraction and electron microscopy, the electron irradiation causes chemical changes in MF2 crystals such as the desorption of fluorine and the accumulation of oxygen in the irradiated area with the formation of oxide MO. The fluorine desorption rate increases significantly when the electron-beam density exceeds the threshold value of ˜2 × 103 pA/cm2). In BaF2 samples, the transformation of BaO into Ba(OH)2 was observed when irradiation stopped. The renewal of irradiation is accompanied by the inverse transformation of Ba(OH)2 into BaO. In the initial stage of irradiation of all MF2 compounds, the oxide phase is in the single-crystal state with a lattice highly matched with the MF2 matrix. When the irradiation dose is increased, the oxide phase passes to the polycrystalline phase. Gaseous products of MF2 destruction (in the form of bubbles several nanometers in diameter) form a rectangular array with a period of ˜20 nm in the sample.

  17. Vibronic transitions in the alkali-metal (Li, Na, K, Rb) - alkaline-earth-metal (Ca, Sr) series: A systematic analysis of de-excitation mechanisms based on the graphical mapping of Frank-Condon integrals

    NASA Astrophysics Data System (ADS)

    Pototschnig, Johann V.; Meyer, Ralf; Hauser, Andreas W.; Ernst, Wolfgang E.

    2017-02-01

    Research on ultracold molecules has seen a growing interest recently in the context of high-resolution spectroscopy and quantum computation. After forming weakly bound molecules from atoms in cold collisions, the preparation of molecules in low vibrational levels of the ground state is experimentally challenging, and typically achieved by population transfer using excited electronic states. Accurate potential energy surfaces are needed for a correct description of processes such as the coherent de-excitation from the highest and therefore weakly bound vibrational levels in the electronic ground state via couplings to electronically excited states. This paper is dedicated to the vibrational analysis of potentially relevant electronically excited states in the alkali-metal (Li, Na, K, Rb)- alkaline-earth metal (Ca,Sr) diatomic series. Graphical maps of Frank-Condon overlap integrals are presented for all molecules of the group. By comparison to overlap graphics produced for idealized potential surfaces, we judge the usability of the selected states for future experiments on laser-enhanced molecular formation from mixtures of quantum degenerate gases.

  18. 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.

  19. 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.

  20. 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.

  1. Multi-stage hydride-hydrogen compressor

    NASA Astrophysics Data System (ADS)

    Golben, P. M.

    A 4-stage metal hydride/hydrogen compressor that uses low temperature hot water (75 C) as its energy source has been built and tested. The compressor utilizes a new hydride heat exchanger technique that has achieved fast cycling time (with 20 C cooling water) on the order of 1 min. This refinement substantially decreases the size, weight and cost of the unit when compared to previous hydride compressors or even conventional mechanical diaphragm compressors.

  2. 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.

  3. Ten degree Kelvin hydride refrigerator

    NASA Technical Reports Server (NTRS)

    Jones, Jack A. (Inventor)

    1987-01-01

    A compact hydride absorption refrigeration system with few moving parts for 10 Kelvin operation is disclosed and comprises liquid hydrogen producing means in combination with means for solidifying and subliming the liquid hydrogen produced. The liquid hydrogen is sublimed at about 10 Kelvin. By using a symmetrical all hydrogen redundant loop system, a 10 Kelvin refrigeration system can be operated for many years with only a fraction of the power required for prior art systems.

  4. 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.

  5. Coinage Metal Hydrides: Synthesis, Characterization, and Reactivity.

    PubMed

    Jordan, Abraham J; Lalic, Gojko; Sadighi, Joseph P

    2016-08-10

    Hydride complexes of copper, silver, and gold encompass a broad array of structures, and their distinctive reactivity has enabled dramatic recent advances in synthesis and catalysis. This Review summarizes the synthesis, characterization, and key stoichiometric reactions of isolable or observable coinage metal hydrides. It discusses catalytic processes in which coinage metal hydrides are known or probable intermediates, and presents mechanistic studies of selected catalytic reactions. The purpose of this Review is to convey how developments in coinage metal hydride chemistry have led to new organic transformations, and how developments in catalysis have in turn inspired the synthesis of reactive new complexes.

  6. Thermodynamic Hydricity of Transition Metal Hydrides.

    PubMed

    Wiedner, Eric S; Chambers, Matthew B; Pitman, Catherine L; Bullock, R Morris; Miller, Alexander J M; Appel, Aaron M

    2016-08-10

    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 bond-breaking 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 H2 heterolysis method involves measuring the equilibrium of heterolytic cleavage of H2 in the presence of a base, and the potential-pKa 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. Methods for using hydricity values to predict chemical reactivity are also discussed, including organic transformations, the reduction of CO2, and the production and oxidation of hydrogen.

  7. Alkaline sorbent injection for mercury control

    DOEpatents

    Madden, Deborah A.; Holmes, Michael J.

    2002-01-01

    A mercury removal system for removing mercury from combustion flue gases is provided in which alkaline sorbents at generally extremely low stoichiometric molar ratios of alkaline earth or an alkali metal to sulfur of less than 1.0 are injected into a power plant system at one or more locations to remove at least between about 40% and 60% of the mercury content from combustion flue gases. Small amounts of alkaline sorbents are injected into the flue gas stream at a relatively low rate. A particulate filter is used to remove mercury-containing particles downstream of each injection point used in the power plant system.

  8. Alkaline sorbent injection for mercury control

    DOEpatents

    Madden, Deborah A.; Holmes, Michael J.

    2003-01-01

    A mercury removal system for removing mercury from combustion flue gases is provided in which alkaline sorbents at generally extremely low stoichiometric molar ratios of alkaline earth or an alkali metal to sulfur of less than 1.0 are injected into a power plant system at one or more locations to remove at least between about 40% and 60% of the mercury content from combustion flue gases. Small amounts of alkaline sorbents are injected into the flue gas stream at a relatively low rate. A particulate filter is used to remove mercury-containing particles downstream of each injection point used in the power plant system.

  9. 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

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

    NASA Astrophysics Data System (ADS)

    Filipek, S. M.; Paul-Boncour, V.; Liu, R. S.; Jacob, I.; Tsutaoka, T.; Budziak, A.; Morawski, A.; Sugiura, H.; Zachariasz, P.; Dybko, K.; Diduszko, R.

    2016-12-01

    Brief summary of our former work on high hydrogen pressure syntheses of novel hydrides and studies of their properties is supplemented with new results. Syntheses and properties of a number of hydrides (unstable, metastable or stable in ambient conditions) derived under high hydrogen pressure from intermetallic compounds, like MeT2, MeNi5, Me7T3, Y6Mn23 and YMn12 (where Me = zirconium, yttrium or rare earth; T = transition metal) are presented. Stabilization of ZrFe2H4 due to surface phenomena was revealed. Unusual role of manganese in hydride forming processes is pointed out. Hydrogen induced phase transitions, suppression of magnetism, antiferromagnetic-ferromagnetic and metal-insulator or semimetal-metal transitions are described. Equations of state (EOS) of hydrides submitted to hydrostatic pressures up to 30 GPa are presented and discussed.

  11. Erbium hydride thermal desorption : controlling kinetics.

    SciTech Connect

    Ferrizz, Robert Matthew

    2007-08-01

    Thermal desorption spectroscopy (TDS) is used to study the decomposition kinetics of erbium hydride thin films. The TDS results presented in this report show that hydride film processing parameters directly impact thermal stability. Issues to be addressed include desorption kinetics for dihydrides and trihydrides, and the effect of film growth parameters, loading parameters, and substrate selection on desorption kinetics.

  12. 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.

  13. Hydrides in Space: Past, Present, and Future

    NASA Astrophysics Data System (ADS)

    Lis, D. C.; Goldsmith, P. F.; Bergin, E. A.; Falgarone, E.; Gerin, M.; Roueff, E.

    2009-12-01

    One of the central questions of modern astrophysics concerns the life cycle of molecules in the Universe—from the diffuse interstellar medium to planetary systems—and the chemical pathways leading from simple atoms and diatomic molecules to complex organic species. In the past two decades, the Caltech Submillimeter Observatory (CSO) has contributed a number of key discoveries on these topics. Light hydrides are of particular interest for astrochemistry, as the basic building blocks of the chemical networks in both diffuse and dense clouds. Ongoing and planned submillimeter wide-field continuum surveys will yield hundreds of potential galactic targets suitable for detailed spectroscopic follow-ups. Recent advances in detector and digital spectrometer technologies promise to truly revolutionize further the field of high-resolution submillimeter spectroscopy and its application to the study of the life cycle of molecules. This will greatly improve our understanding of astrochemistry, astrobiology, the origin of life on Earth, and allow assessing the possibilities of life in other planetary systems.

  14. Alkali-metal/alkaline-earth-metal fluorine beryllium borate NaSr3Be3B3O9F4 with large nonlinear optical properties in the deep-ultraviolet region

    NASA Astrophysics Data System (ADS)

    Reshak, A. H.; Huang, Hongwei; Kamarudin, H.; Auluck, S.

    2015-02-01

    The linear optical response and second harmonic generation (SHG) in alkali-metal/alkaline-earth-metal fluorine beryllium borate NaSr3Be3B3O9F4 are investigated by means of density functional theory. Calculations are performed using four types of exchange correlations: Ceperley-Alder local density approximation, Perdew Burke and Ernzerhof general gradient approximation, Engel-Vosko generalized gradient approximation, and the recently modified Becke-Johnson potential (mBJ). The mBJ approach brings the calculated band gap (7.20 eV) in excellent agreement with the experimental one (7.28 eV). The calculated values of the uniaxial anisotropy δɛ=-0.076 and the birefringence Δn (0 ) =0.052 indicate considerable anisotropy in the linear optical properties, which makes it favorable for the second harmonic generation. The dominant component of the second harmonic generation is χ111(2)(ω) . The value of |χ111(2)(ω) | is about 1.2 pm/V at λ = 1064 nm in agreement with previous calculations. To analyze the origin of the high SHG of NaSr3Be3B3O9F4 single crystals, we have correlated the features of |χ111(2)(ω) | spectra with the features of ɛ2(ω) spectra as a function of ω/2 and ω. From the calculated dominant component |χ111(2)(ω) | , we find that the microscopic first hyperpolarizability, β111 , the vector components along the dipole moment direction is 0.5 × 10-30 esu at static limit and 0.6 × 10-30 esu at λ = 1064 nm.

  15. The influence of different alkaline earth oxides on the structural and optical properties of undoped, Ce-doped, Sm-doped, and Sm/Ce co-doped lithium alumino-phosphate glasses

    NASA Astrophysics Data System (ADS)

    Othman, H. A.; Arzumanyan, G. M.; Möncke, D.

    2016-12-01

    Undoped, singly Sm doped, Ce doped, and Sm/Ce co-doped lithium alumino-phosphate glasses with different alkaline earth modifiers were prepared by melt quenching. The structure of the prepared glasses was investigated by FT-IR and Raman, as well as by optical spectroscopy. The effect of the optical basicity of the host glass matrix on the added active dopants was studied, as was the effect doping had on the phosphate structural units. The optical edge shifts toward higher wavelengths with an increase in the optical basicity due to the increased polarizability of the glass matrix, but also with increasing CeO2 concentration as a result of Ce3+/Ce4+ inter valence charge transfer (IV-CT) absorption. The optical band gap for direct and indirect allowed transitions was calculated for the undoped glasses. The glass sample containing Mg2+ modifier ions is found to have the highest value (4.16 eV) for the optical band gap while Ba2+ has the lowest value (3.61 eV). The change in the optical band gap arises from the structural changes and the overall polarizability (optical basicity). Refractive index, molar refractivity Rm and molar polarizability αm values increase with increasing optical basicity of the glasses. The characteristic absorption peaks of Sm3+ were also investigated. For Sm/Ce co-doped glasses, especially at high concentration of CeO2, the absorption of Ce3+ hinders the high energy absorption of Sm3+ and this effect becomes more obvious with increasing optical basicity.

  16. CRADA (AL-C-2009-02) Final Report: Phase I. Lanthanum-based Start Materials for Hydride Batteries

    SciTech Connect

    Gschneidner, Jr., Karl; Schmidt, Frederick; Frerichs, A. E.; Ament, Katherine A.

    2013-05-01

    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{sub 1-x}R{sub x})(Ni{sub 1-y}M{sub y})(Si{sub 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.

  17. 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.

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

    PubMed

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

    2017-04-12

    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.

  19. Zirconium hydride containing explosive composition

    DOEpatents

    Walker, Franklin E.; Wasley, Richard J.

    1981-01-01

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

  20. Optical properties of metal-hydride switchable films

    NASA Astrophysics Data System (ADS)

    Griessen, Ronald

    2001-03-01

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

  1. 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.

  2. Positron elastic scattering from alkaline earth targets

    NASA Astrophysics Data System (ADS)

    Poveda, Luis A.; Assafrão, Denise; Mohallem, José R.

    2016-07-01

    A previously reported model potential approach [Poveda et al., Phys. Rev. A 87, 052702 (2013)] was extended to study low energy positron elastic scattering from beryllium and magnesium. The cross sections were computed for energies ranging from 10-5 eV up to well above the positronium formation threshold. The present results are in good agreement with previous reports, including the prediction of a p-wave resonance in the cross section for magnesium. The emergence of this shape resonance is connected to a trend observed in the evolution of the partial wave cross section in going from Be to Mg target. This trend lead us to speculate that a sharp d-wave resonance should be observed in positron elastic scattering from calcium. The positron-target binding energies are investigated in detail, both using the scattering information and by direct computation of the bound state energies using the model potentials. Contribution to the Topical Issue "Advances in Positron and Electron Scattering", edited by Paulo Limao-Vieira, Gustavo Garcia, E. Krishnakumar, James Sullivan, Hajime Tanuma and Zoran Petrovic.Supplementary material in the form of one pdf file available from the Journal web page at http://dx.doi.org/10.1140/epjd/e2016-70120-y

  3. Alkaline earth stannates: The next silicon?

    SciTech Connect

    Ismail-Beigi, Sohrab Ahn, Charles H.; Walker, Frederick J.; Cheong, Sang-Wook; Rabe, Karin M.

    2015-06-01

    Semiconductor materials are being used in an increasingly diverse array of applications, with new device concepts being proposed each year for solar cells, flat-panel displays, sensors, memory, and spin transport. This rapid progress of invention outpaces the development of new semiconductor materials with the required properties and performance. In many applications, high carrier mobility at room temperature is required in addition to specific functional properties critical to the device concept. We review recent developments on high mobility stannate perovskite oxide materials and devices.

  4. Electrical Resistivity of Alkaline Earth Elements.

    DTIC Science & Technology

    1976-12-01

    and Alloys ," Volume 12 of Thermophysical Properties of Matter - The TPRC Data Series, Plenum Press, New York, 1440 pp., 1975. (T80643) 2. Matthiessen, A...1964. (E17556) 48. Seth, R. S. and Woods, S. B., "Electrical Resistivity and Deviations from Matthiessen’s Rule in Dilute Alloys of Aluminum , Cadmium...Resistance of Dilute Magnesium and Aluminum Alloys at Low Temperature," Can. J. of Phys. 38(3), 376-84, 1960. (E14737) 57. Schofield, F. H., "The

  5. PARAMAGNETIC PROPERTIES OF THE ALKALINE EARTH FLUORIDES.

    DTIC Science & Technology

    constants for Mn(2+) in CaF2 and SrF2 were measured over the temperature range 77 to 850K. In both cases the magnitude of the hyperfine coupling constant...decreases with increasing temperature; and the temperature dependance is stronger for SrF2 . The results have been interpreted using the Simanek-Orbach theory of a phonon-induced hyperfine field. (Author)

  6. Absorption Coefficient of Alkaline Earth Halides.

    DTIC Science & Technology

    1980-04-01

    levels . As a natural consequence, the magnitude of the absorption coefficient is the key parameter in selecting laser window materials. Over the past...of as can be achieved through improved crystal growing techniques and surface polishing. 2.5. Urbach’s Rule A central question for the development of...high absorption levels , inaccuracies progressively increasing with decreasing absorption level , a natural consequence of decreasing in instrumental

  7. Hydrogen-storing hydride complexes

    DOEpatents

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

    2012-04-10

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

  8. 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.

  9. 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.

  10. High-pressure synthesis of lithium hydride

    NASA Astrophysics Data System (ADS)

    Howie, Ross T.; Narygina, Olga; Guillaume, Christophe L.; Evans, Shaun; Gregoryanz, Eugene

    2012-08-01

    By compressing elemental lithium and hydrogen in a diamond anvil cell, we have synthesized lithium hydride (LiH) at pressures as low as 50 MPa at room temperature. Combined Raman spectroscopy and synchrotron x-ray diffraction measurements reveal that, once synthesized, LiH remains stable at 300 K up to 160 GPa in the presence of molecular hydrogen. The mixture of lithium hydride and molecular hydrogen and application of pressure alone cannot form a higher H2 content hydride (LiHx, x>1) as was suggested from the theoretical ab initio calculations and therefore, cannot be considered as a route to low-pressure hydrogen rich material metallization.

  11. Computational Modeling of Uranium Hydriding and Complexes

    SciTech Connect

    Balasubramanian, K; Siekhaus, W J; McLean, W

    2003-02-03

    Uranium hydriding is one of the most important processes that has received considerable attention over many years. Although many experimental and modeling studies have been carried out concerning thermochemistry, diffusion kinetics and mechanisms of U-hydriding, very little is known about the electronic structure and electronic features that govern the U-hydriding process. Yet it is the electronic feature that controls the activation barrier and thus the rate of hydriding. Moreover the role of impurities and the role of the product UH{sub 3} on hydriding rating are not fully understood. An early study by Condon and Larson concerns with the kinetics of U-hydrogen system and a mathematical model for the U-hydriding process. They proposed that diffusion in the reactant phase by hydrogen before nucleation to form hydride phase and that the reaction is first order for hydriding and zero order for dehydriding. Condon has also calculated and measures the reaction rates of U-hydriding and proposed a diffusion model for the U-hydriding. This model was found to be in excellent agreement with the experimental reaction rates. From the slopes of the Arrhenius plot the activation energy was calculated as 6.35 kcal/mole. In a subsequent study Kirkpatrick formulated a close-form for approximate solution to Condon's equation. Bloch and Mintz have proposed the kinetics and mechanism for the U-H reaction over a wide range of pressures and temperatures. They have discussed their results through two models, one, which considers hydrogen diffusion through a protective UH{sub 3} product layer, and the second where hydride growth occurs at the hydride-metal interface. These authors obtained two-dimensional fits of experimental data to the pressure-temperature reactions. Kirkpatrick and Condon have obtained a linear solution to hydriding of uranium. These authors showed that the calculated reaction rates compared quite well with the experimental data at a hydrogen pressure of 1 atm. Powell

  12. New alkaline earth-zirconium oxalates M2Zr(C 2O 4) 4· nH 2O ( M=Ba, Sr, Ca) synthesis, crystal structure and thermal behavior

    NASA Astrophysics Data System (ADS)

    Chapelet-Arab, B.; Nowogrocki, G.; Abraham, F.; Grandjean, S.

    2004-11-01

    Three new alkaline earth-zirconium oxalates M2Zr(C 2O 4) 4· nH 2O have been synthesized by precipitation methods for M=Ba, Sr, Ca. For each compound the crystal structure was determined from single crystals obtained by controlled diffusion of M 2+ and Zr 4+ ions through silica gel containing oxalic acid. Ba 2Zr(C 2O 4) 4·7H 2O, monoclinic, space group C2/c, a=9.830(2), b=29.019(6), c=9.178(2) Å, β=122.248(4) °, V=2214.2(8) Å, Z=4, R=0.0427; Sr 2Zr(C 2O 4) 4·11H 2O, tetragonal, space group I41/acd, a=16.139(4), c=18.247(6) Å, V=4753(2) Å,Z=8, R=0.0403; Ca 2Zr(C 2O 4) 4·5H 2O, orthorhombic, space group Pna2 1, a=8.4181(5), b=15.8885(8), c=15.8885(8) Å, V=2125(2) Å, Z=4, R=0.0622. The structures of the three compounds consist of chains of edge-shared MO 6(H 2O) x ( x=2 or 3) polyhedra connected to ZrO 8 polyhedra through oxalate groups. Depending on the arrangement of chains, the ZrO 8 polyhedron geometry (dodecahedron or square antiprism) and the connectivity, two types of three-dimensional frameworks are obtained. For the smallest M2+ cations (Sr 2+, Ca 2+), large tunnels are obtained, running down the c direction of the unit cell, which can accommodate zeolitic water molecules. For the largest Ba 2+ cation, the second framework is formed and is closely related to that of Pb 2Zr(C 2O 4) 4· nH 2O. The decomposition at 800°C into strontium carbonate, barium carbonate or calcium oxide and MZrO 3 ( M=Sr, Ba, Ca) perovskite is reported from thermal analyses studies and high temperature X-ray powder diffraction.

  13. New alkaline earth-zirconium oxalates M{sub 2}Zr(C{sub 2}O{sub 4}){sub 4}.nH{sub 2}O (M=Ba, Sr, Ca) synthesis, crystal structure and thermal behavior

    SciTech Connect

    Chapelet-Arab, B.; Abraham, F. . E-mail: francis.abraham@ensc-lille.fr; Grandjean, S.

    2004-11-01

    Three new alkaline earth-zirconium oxalates M{sub 2}Zr(C{sub 2}O{sub 4}){sub 4}.nH{sub 2}O have been synthesized by precipitation methods for M=Ba, Sr, Ca. For each compound the crystal structure was determined from single crystals obtained by controlled diffusion of M{sup 2+} and Zr{sup 4+} ions through silica gel containing oxalic acid. Ba{sub 2}Zr(C{sub 2}O{sub 4}){sub 4}.7H{sub 2}O, monoclinic, space group C2/c, a=9.830(2), b=29.019(6), c=9.178(2)A, {beta}=122.248(4){sup o}, V=2214.2(8)A3, Z=4, R=0.0427; Sr{sub 2}Zr(C{sub 2}O{sub 4}){sub 4}.11H{sub 2}O, tetragonal, space group I41/acd, a=16.139(4), c=18.247(6)A, V=4753(2)A3, Z=8, R=0.0403; Ca{sub 2}Zr(C{sub 2}O{sub 4}){sub 4}.5H{sub 2}O, orthorhombic, space group Pna2{sub 1}, a=8.4181(5), b=15.8885(8), c=15.8885(8)A, V=2125(2)A3, Z=4, R=0.0622. The structures of the three compounds consist of chains of edge-shared MO{sub 6}(H{sub 2}O){sub x} (x=2 or 3) polyhedra connected to ZrO{sub 8} polyhedra through oxalate groups. Depending on the arrangement of chains, the ZrO{sub 8} polyhedron geometry (dodecahedron or square antiprism) and the connectivity, two types of three-dimensional frameworks are obtained. For the smallest M{sup 2+} cations (Sr{sup 2+}, Ca{sup 2+}), large tunnels are obtained, running down the c direction of the unit cell, which can accommodate zeolitic water molecules. For the largest Ba{sup 2+} cation, the second framework is formed and is closely related to that of Pb{sub 2}Zr(C{sub 2}O{sub 4}){sub 4}.nH{sub 2}O. The decomposition at 800{sup o}C into strontium carbonate, barium carbonate or calcium oxide and MZrO{sub 3} (M=Sr, Ba, Ca) perovskite is reported from thermal analyses studies and high temperature X-ray powder diffraction.

  14. Method of forming metal hydride films

    NASA Technical Reports Server (NTRS)

    Steinberg, R.; Alger, D. L.; Cooper, D. W. (Inventor)

    1977-01-01

    The substrate to be coated (which may be of metal, glass or the like) is cleaned, both chemically and by off-sputtering in a vacuum chamber. In an ultra-high vacuum system, vapor deposition by a sublimator or vaporizer coats a cooled shroud disposed around the substrate with a thin film of hydride forming metal which getters any contaminant gas molecules. A shutter is then opened to allow hydride forming metal to be deposited as a film or coating on the substrate. After the hydride forming metal coating is formed, deuterium or other hydrogen isotopes are bled into the vacuum system and diffused into the metal film or coating to form a hydride of metal film. Higher substrate temperatures and pressures may be used if various parameters are appropriately adjusted.

  15. 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.

  16. 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.

  17. 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

  18. Anodes for alkaline electrolysis

    DOEpatents

    Soloveichik, Grigorii Lev

    2011-02-01

    A method of making an anode for alkaline electrolysis cells includes adsorption of precursor material on a carbonaceous material, conversion of the precursor material to hydroxide form and conversion of precursor material from hydroxide form to oxy-hydroxide form within the alkaline electrolysis cell.

  19. Hydride fuel behavior in LWRs

    NASA Astrophysics Data System (ADS)

    Olander, Donald R.; Ng, Marowen

    2005-11-01

    The U-Zr hydride U 0.31ZrH 1.6 offers a number of advantages over oxide fuel for light-water reactors. Fission-gas release appears to be very small (release fraction ˜10 -4) up to 600 °C, which is close to the maximum fuel temperature. Initial irradiation-induced swelling can be as large as 5% for temperatures exceeding 650 °C. Hydrogen redistributes due to the non-uniform temperature in the fuel from the as-fabricated H/Zr of 1.6 to one that is higher at the pellet periphery than at the centerline. Radial redistribution produces 'hydrogen' stresses in the pellet which add to the usual thermal stresses. In a helium-bonded fuel rod, the total stresses are less than the fracture stress; in a liquid-metal-bonded fuel rod, the fracture stress is exceeded in the central portion of the pellet, but the surface remains in compression. Axial redistribution moves substantial quantities of hydrogen from the middle portion of the fuel stack to the ends. The neutronic effect of this displacement of the moderator is unknown.

  20. Metal Hydride Heat Storage Technology for Directed Energy Weapon Systems

    DTIC Science & Technology

    2007-11-16

    over time after the pulse operation. A compressor -driven metal hydride heat storage system was developed for efficient, compact heat storage and...principle and heat storage performance results of the compressor -driven metal hydride heat storage system through system modeling and prototype testing. The...hyd/m³] Subscripts A Metal hydride reactor B Hydrogen container C Hydrogen compressor s Hydrogen solid phase in hydride f Hydrogen fluid phase

  1. 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...

  2. 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...

  3. 49 CFR 173.311 - Metal hydride storage systems.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 49 Transportation 2 2012-10-01 2012-10-01 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...

  4. 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...

  5. Alkaline battery operational methodology

    DOEpatents

    Sholklapper, Tal; Gallaway, Joshua; Steingart, Daniel; Ingale, Nilesh; Nyce, Michael

    2016-08-16

    Methods of using specific operational charge and discharge parameters to extend the life of alkaline batteries are disclosed. The methods can be used with any commercial primary or secondary alkaline battery, as well as with newer alkaline battery designs, including batteries with flowing electrolyte. The methods include cycling batteries within a narrow operating voltage window, with minimum and maximum cut-off voltages that are set based on battery characteristics and environmental conditions. The narrow voltage window decreases available capacity but allows the batteries to be cycled for hundreds or thousands of times.

  6. Iron Group Hydrides in Noyori Bifunctional Catalysis.

    PubMed

    Morris, Robert H

    2016-12-01

    This is an overview of the hydride-containing catalysts prepared in the Morris group for the efficient hydrogenation of simple ketones, imines, nitriles and esters and the asymmetric hydrogenation and transfer hydrogenation of prochiral ketones and imines. The work was inspired by and makes use of Noyori metal-ligand bifunctional concepts involving the hydride-ruthenium amine-hydrogen HRuNH design. It describes the synthesis and some catalytic properties of hydridochloro, dihydride and amide complexes of ruthenium and in one case, osmium, with monodentate, bidentate and tetradentate phosphorus and nitrogen donor ligands. The iron hydride that has been identified in a very effective asymmetric transfer hydrogenation process is also mentioned. The link between the HMNH structure and the sense of enantioinduction is demonstrated by use of simple transition state models.

  7. 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

  8. Light Weight Design Nickel-Alkaline Cells Using Fiber Electrodes

    NASA Technical Reports Server (NTRS)

    Pickett, David F.; Willis, Bob; Britton, Doris; Saelens, Johan

    2005-01-01

    Using fiber electrode technology, currently produced by Bekaert Corporation (Bekaert), Electro Energy, Inc., (EEI) Mobile Energy Products Group (formerly, Eagle-Picher Technologies, LLC., Power Systems Department) in Colorado Springs, CO has demonstrated that it is feasible to manufacture flight weight nickel-hydrogen cells having about twice the specific energy (80 vs. 40 watt-hr/kg) as state-of-the-art nickel-hydrogen cells that are flown on geosynchronous communications satellites. Although lithium-ion battery technology has made large in-roads to replace the nickel-alkaline technology (nickel-cadmium, nickel-metal hydride), the technology offered here competes with lithium-ion weight and offers alternatives not present in the lithium-ion chemistry such as ability to undergo continuous overcharge, reversal on discharge and sustain rate capability sufficient to start automotive and aircraft engines at subzero temperatures. In development to date seven 50 ampere-hour nickel-hydrogen have been constructed, acceptance tested and briefly tested in a low earth orbit (LEO) cycle regime. The effort was jointly funded by Electro Energy, Inc. and NASA Glenn Research Center, Cleveland, OH. Five of the seven cells have been shipped to NASA GRC for further cycle testing. Two of the cells experienced failure due to internal short circuits during initial cycle testing at EEL Destructive Physical Analysis (DPA) of one of the cells has shown the failure mode to be due to inadequate hydrogen catalyst electrodes that were not capacity balanced with the higher energy density nickel oxide electrodes. In the investigators opinion, rebuild of the cells using proper electrode balance would result in cells that could sustain over 30,000 cycles at moderate depths-of-discharge in a LEO regime or endure over 20 years of geosynchronous orbit (GEO) cycling while realizing a two-fold increase in specific energy for the battery or a 1.1 kg weight savings per 50 ampere-hour cell. Additional

  9. Hydride formation on deformation twin in zirconium alloy

    NASA Astrophysics Data System (ADS)

    Kim, Ju-Seong; Kim, Sung-Dae; Yoon, Jonghun

    2016-12-01

    Hydrides deteriorate the mechanical properties of zirconium (Zr) alloys used in nuclear reactors. Intergranular hydrides that form along grain boundaries have been extensively studied due to their detrimental effects on cracking. However, it has been little concerns on formation of Zr hydrides correlated with deformation twins which is distinctive heterogeneous nucleation site in hexagonal close-packed metals. In this paper, the heterogeneous precipitation of Zr hydrides at the twin boundaries was visualized using transmission electron microscopy. It demonstrates that intragranular hydrides in the twinned region precipitates on the rotated habit plane by the twinning and intergranular hydrides precipitate along the coherent low energy twin boundaries independent of the conventional habit planes. Interestingly, dislocations around the twin boundaries play a substantial role in the nucleation of Zr hydrides by reducing the misfit strain energy.

  10. 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##

  11. Ductility Evaluation of As-Hydrided and Hydride Reoriented Zircaloy-4 Cladding under Simulated Dry-Storage Condition

    SciTech Connect

    Yan, Yong; Plummer, Lee K; Ray, Holly B; Cook, Tyler S; Bilheux, Hassina Z

    2014-01-01

    Pre-storage drying-transfer operations and early stage storage expose cladding to higher temperatures and much higher pressure-induced tensile hoop stresses relative to normal operation in-reactor and pool storage under these conditions. Radial hydrides could precipitate during slow cooling and provide an additional embrittlement mechanism as the cladding temperature decreases below the ductile-to-brittle transition temperature. As a means of simulating this behavior, unirradiated hydrided Zircaloy-4 samples were fabricated by a gas charging method to levels that encompass the range of hydrogen concentrations observed in current used fuel. Mechanical testing was carried out by the ring compression test (RCT) method at various temperatures to evaluate the sample s ductility for both as-hydrided and post-hydride reorientation treated specimens. As-hydrided samples with higher hydrogen concentration (>800 ppm) resulted in lower strain before fracture and reduced maximum load. Increasing RCT temperatures resulted in increased ductility of the as-hydrided cladding. A systematic radial hydride treatment was conducted at various pressures and temperatures for the hydrided samples with H content around 200 ppm. Following the radial hydride treatment, RCTs on the hydride reoriented samples were conducted and exhibited lower ductility compared to as-hydrided samples.

  12. A thermokinetically driven metal-hydride actuator

    NASA Astrophysics Data System (ADS)

    Jung, Kwangmok; Kim, Kwang J.

    2008-03-01

    The purpose of this study is to develop a novel thermokinetically-driven actuator technology based on the physics of metal hydrides (MH's). A metal hydride absorbs and desorbs hydrogen due to the imposed temperature swing(s). The MH can also work as an effective thermally-driven hydrogen compressor producing more than 5,000 psia net pressure swing. The MH actuation system can be built in a simple structure, exhibits high power, produces soft actuating, and is essentially noiseless. Moreover, it is much more powerful and compact than conventional pneumatic systems that require bulky auxiliary systems. It is our belief that the MH actuators are useful for many emerging industrial, biorobotic, and civil structural applications. In this paper, we report the recent preliminary experimental results for a laboratory-prototyped MH actuation system. In particular, the dynamic response characteristics, enhanced controllability, thermodynamic performances, and reliability of the metal hydride actuator were studied in order to estimate the actuation capability of the MH actuator. A unique design of the MH actuator was created. It encases a so-called "porous metal hydride (PMH)" in the reactor to effectively achieve desirable performance by improving overall thermal conductance.

  13. X-Ray Topography of Hydride Domains.

    DTIC Science & Technology

    1983-04-01

    boundaries between hydride (deuteride) domains, and the irregular boundaries correspond to incoherent twin boundaries . Trace analysis of the coherent...topographs of the NbHo.78 and NbO 0 .75 crystals. As discussed by Schober and Linke (1976b), the straight boundaries correspond to coherent twin

  14. Metal hydride fuel storage and method thereof

    DOEpatents

    Morse, Jeffrey D.; Jankowski, Alan F.; Yu, Conrad

    2006-10-17

    Disclosed herein is a metal hydride fuel storage cartridge having integrated resistive heaters that can be used in conjunction with fuel cells such as MEMS-based fuel cells. The cartridge is fabricated using micromachining methods and thin/thick film materials synthesis techniques.

  15. Metal hydride fuel storage and method thereof

    DOEpatents

    Morse, Jeffrey D [Martinez, CA; Jankowski, Alan F [Livermore, CA; Yu, Conrad [Antioch, CA

    2009-05-05

    Disclosed herein is a metal hydride fuel storage cartridge having integrated resistive heaters that can be used in conjunction with fuel cells such as MEMS-based fuel cells. The cartridge is fabricated using micromachining methods and thin/thick film materials synthesis techniques.

  16. Alkaline flooding injection strategy

    SciTech Connect

    French, T.R.; Josephson, C.B.

    1992-03-01

    The objective of this project is to improved alkali-surfactant flooding methods, and this includes determining the proper design of injection strategy. Several different injection strategies have been used or suggested for recovering heavy oils with surfactant-enhanced alkaline flooding methods. Oil recovery was compared for four different injection strategies: (1) surfactant followed by polymer, (2) surfactant followed by alkaline polymer, (3) alkaline surfactant followed by polymer, and (4) alkali, surfactant, and polymer mixed in a single formulation. The effect of alkaline preflush was also studied under two different conditions. All of the oil recovery experiments were conducted under optimal conditions with a viscous, non-acidic oil from Hepler (KS) oil field. The coreflood experiments were conducted with Berea sandstone cores since field core was not available in sufficient quantity for coreflood tests. The Tucker sand of Hepler field is a Class I fluvial dominated deltaic reservoir, as classified by the Department of Energy, which has been selected as the site of a DOE-sponsored field pilot test.

  17. 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.

  18. Synthesis and properties of platinum hydride

    NASA Astrophysics Data System (ADS)

    Scheler, Thomas; Degtyareva, Olga; Marqués, Miriam; Guillaume, Christophe L.; Proctor, John E.; Evans, Shaun; Gregoryanz, Eugene

    2011-06-01

    Synchrotron x-ray diffraction experiments on compressed platinum-hydrogen mixtures reveal the formation of platinum hydride at a pressure of 27(1) GPa at room temperature. This compound exhibits two phases, PtH-I and PtH-II, coexisting up to the pressure of 42 GPa, above which the single phase of PtH-II is observed. Pt atoms in the PtH-II phase are shown to form a hexagonal closed-packed structure. This phase exhibits a high bulk modulus of 310 (10) GPa and is stable up to at least 53 GPa. Ab initio calculations show that PtH-II is superconducting with Tc = 12 K at 90 GPa, the highest temperature of superconducting transition among any known metal hydride.

  19. Unoccupied electronic states in cerium hydrides

    NASA Astrophysics Data System (ADS)

    Osterwalder, J.; Schlapbach, L.

    1985-05-01

    We present UV isochromat spectra of polycrystalline CeH 2.1 and CeH 2.9. The intensity at EF is small in CeH 2.1 and vanishes in CeH 2.9 as it is expected from XPS, UPS and conductivity data. In both hydrides broad features (≈2 eV FWHM) appear between 4 and 5 eV above EF. This is in qualitative agreement with bandstructure calculations.

  20. Dissipative hydride precipitates in superconducting niobium cavities

    SciTech Connect

    Romanenko, A.; Cooley, L.D.; Ciovati, G.; Wu, G.; /Argonne

    2011-10-01

    We report the first direct observation of the microstructural features exhibiting RF losses at high surface magnetic fields of above 100 mT in field emission free superconducting niobium cavities. The lossy areas were identified by advanced thermometry. Surface investigations using different techniques were carried out on cutout samples from lossy areas and showed the presence of dendritic niobium hydrides. This finding has possible implications to the mechanisms of RF losses in superconducting niobium at all field levels.

  1. Materials compatibility of hydride storage materials with austenitic stainless steels

    SciTech Connect

    Clark, E.A.

    1992-09-21

    This task evaluated the materials compatibility of LaNi[sub 5-x]Al[sub x] (x= 0.3, 0.75) hydrides and palladium coated kieselguhr with austenitic stainless steel in hydrogen and tritium process environments. Based on observations of retired prototype hydride storage beds and materials exposure testing samples designed for this study, no materials compatibility problem was indicated. Scanning electron microscopy observations of features on stainless steel surfaces after exposure to hydrides are also commonly found on as-received materials before hydriding. These features are caused by either normal heat treating and acid cleaning of stainless steel or reflect the final machining operation.

  2. Materials compatibility of hydride storage materials with austenitic stainless steels

    SciTech Connect

    Clark, E.A.

    1992-09-21

    This task evaluated the materials compatibility of LaNi{sub 5-x}Al{sub x} (x= 0.3, 0.75) hydrides and palladium coated kieselguhr with austenitic stainless steel in hydrogen and tritium process environments. Based on observations of retired prototype hydride storage beds and materials exposure testing samples designed for this study, no materials compatibility problem was indicated. Scanning electron microscopy observations of features on stainless steel surfaces after exposure to hydrides are also commonly found on as-received materials before hydriding. These features are caused by either normal heat treating and acid cleaning of stainless steel or reflect the final machining operation.

  3. 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.

  4. 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.

  5. METAL HYDRIDE HYDROGEN COMPRESSORS: A REVIEW

    SciTech Connect

    Bowman Jr, Robert C; Yartys, Dr. Volodymyr A.; Lototskyy, Dr. Michael V; Pollet, Dr. B.G.

    2014-01-01

    Metal hydride (MH) thermal sorption compression is an efficient and reliable method allowing a conversion of energy from heat into a compressed hydrogen gas. The most important component of such a thermal engine the metal hydride material itself should possess several material features in order to achieve an efficient performance in the hydrogen compression. Apart from the hydrogen storage characteristics important for every solid H storage material (e.g. gravimetric and volumetric efficiency of H storage, hydrogen sorption kinetics and effective thermal conductivity), the thermodynamics of the metal-hydrogen systems is of primary importance resulting in a temperature dependence of the absorption/desorption pressures). Several specific features should be optimized to govern the performance of the MH-compressors including synchronisation of the pressure plateaus for multi-stage compressors, reduction of slope of the isotherms and hysteresis, increase of cycling stability and life time, together with challenges in system design associated with volume expansion of the metal matrix during the hydrogenation. The present review summarises numerous papers and patent literature dealing with MH hydrogen compression technology. The review considers (a) fundamental aspects of materials development with a focus on structure and phase equilibria in the metal-hydrogen systems suitable for the hydrogen compression; and (b) applied aspects, including their consideration from the applied thermodynamic viewpoint, system design features and performances of the metal hydride compressors and major applications.

  6. Plasmonic hydrogen sensing with nanostructured metal hydrides.

    PubMed

    Wadell, Carl; Syrenova, Svetlana; Langhammer, Christoph

    2014-12-23

    In this review, we discuss the evolution of localized surface plasmon resonance and surface plasmon resonance hydrogen sensors based on nanostructured metal hydrides, which has accelerated significantly during the past 5 years. We put particular focus on how, conceptually, plasmonic resonances can be used to study metal-hydrogen interactions at the nanoscale, both at the ensemble and at the single-nanoparticle level. Such efforts are motivated by a fundamental interest in understanding the role of nanosizing on metal hydride formation processes in the quest to develop efficient solid-state hydrogen storage materials with fast response times, reasonable thermodynamics, and acceptable long-term stability. Therefore, a brief introduction to the thermodynamics of metal hydride formation is also given. However, plasmonic hydrogen sensors not only are of academic interest as research tool in materials science but also are predicted to find more practical use as all-optical gas detectors in industrial and medical applications, as well as in a future hydrogen economy, where hydrogen is used as a carbon free energy carrier. Therefore, the wide range of different plasmonic hydrogen sensor designs already available is reviewed together with theoretical efforts to understand their fundamentals and optimize their performance in terms of sensitivity. In this context, we also highlight important challenges to be addressed in the future to take plasmonic hydrogen sensors from the laboratory to real applications in devices, including poisoning/deactivation of the active materials, sensor lifetime, and cross-sensitivity toward other gas species.

  7. Nitrogen isotope evidence for alkaline lakes on late Archean continents

    NASA Astrophysics Data System (ADS)

    Stüeken, E. E.; Buick, R.; Schauer, A. J.

    2015-02-01

    Nitrogen isotope ratios in ancient sedimentary rocks are generally interpreted as a proxy for metabolic nitrogen pathways and the redox state of the water column. Fractionation processes occurring under anoxic, alkaline conditions during the dissociation of NH4+ to H+ and volatile NH3 are frequently overlooked, although this mechanism imparts large isotopic fractionations. Here we propose that NH3 volatilization is largely responsible for δ15N values of up to + 50 ‰ at high C/N ratios in the late Archean Tumbiana Formation. This sequence of sedimentary rocks represents a system of lakes that formed on subaerial flood basalts and were partly filled by basaltic volcanic ash. Aqueous alteration of volcanic glass followed by evaporative concentration of ions should have led to the development of high alkalinity with a pH of 9 or higher, as in modern analogues. In this sedimentologically unusual setting, nitrogen isotope ratios thus provide indirect evidence for the oldest alkaline lake system in the rock record. These very heavy lacustrine δ15N values contrast markedly with those of Archean marine sedimentary rocks, making a Precambrian "soda ocean" unlikely. Today, alkaline lakes are among the most productive ecosystems on Earth. Some nutrients, in particular molybdenum, are more soluble at high pH, and certain prebiotic reactions would likely have been favored under alkaline conditions in similar settings earlier in Earth's history. Hence alkaline lakes in the Archean could have been significant for the origin and early evolution of life.

  8. Hydride phase formation in carbon supported palladium hydride nanoparticles by in situ EXAFS and XRD

    NASA Astrophysics Data System (ADS)

    Bugaev, A. L.; Guda, A. A.; Lomachenko, K. A.; Lazzarini, A.; Srabionyan, V. V.; Vitillo, J. G.; Piovano, A.; Groppo, E.; Bugaev, L. A.; Soldatov, A. V.; Dmitriev, V. P.; Pellegrini, R.; van Bokhoven, J. A.; Lamberti, C.

    2016-05-01

    In the current work we present a detailed analysis of the hydride phase formation in industrial Pd/C nanocatalysts by means of combined in situ X-ray absorption spectroscopy (EXAFS), X-ray diffraction (XRD) and volumetric measurements for the temperatures from - 10 to 50 °C in the hydrogen pressure range from 0 to 1000 mbar. α- and β- hydride phases are clearly distinguished in XRD. For the first time, H/Pd atomic ratio were obtained by theoretical fitting of the near-edge region of the absorption spectra (XANES) and compared with volumetric measurements.

  9. Advanced alkaline water electrolysis

    NASA Astrophysics Data System (ADS)

    Wakabayashi, N.; Torikai, E.; Kawami, Y.; Takenaka, H.

    Results are presented of experimental studies of possible separators and electrodes for use in advanced, high-temperature, high-pressure alkaline water electrolyzers. Material evaluations in alkaline water electrolyzers at temperatures from 100 to 120 C have shown a new type polytetrafluoroethylene membrane impregnated with potassium titanate to be the most promising when the separator is prepared by the hydrothermal treatment of a porous PFTE membrane impregnated with hydrated titanium oxide. Measurements of cell voltages in 30% KOH at current densities from 5 to 100 A/sq dm at temperatures up to 120 C with nickel electrodes of various structures have shown the foamed nickel electrode, with an average pore size of 1-1.5 mm, to have the best performance. When the foamed nickel is coated by fine powdered nickel, carbonyl nickel or Raney nickel to increase electrode surface areas, even lower cell voltages were found, indicating better performance.

  10. The sulphate-reduction alkalinity pump tested

    NASA Astrophysics Data System (ADS)

    Meister, Patrick; Petrishcheva, Elena

    2016-04-01

    Carbonate precipitation has been suggested to be induced by alkalinity increase during sulphate reduction under anoxic conditions. This mechanism may explain the formation of carbonate deposits in shallow marine environments, either within a redox stratified sediment inhabited by phototrophic microbial mats or in shallow water within the photic zone where sulphidic water is upwelling onto the shelf. The alkalinity pump may work as long as the sulphide is not reoxidized to sulphate, a process that would acidify the surrounding. The alkalinity effect of sulphate reduction was recently tested by Aloisi (2008) for microbial mats using a model approach. He found that sulphate reduction does not significantly increase or even decrease carbonate saturation and is unlikely to have played a significant role through Earth history. The model considers many environmental factors, including the effect of carbonate precipitation itself on the carbonate equilbrium and on the alkalinity. We used a modified version of Aloisi's (2008) model to simulate the saturation states of aragonite, calcite and dolomite without the effects of carbonate precipitation. This is necessary to evaluate the effect of microbial metabolisms exclusively on carbonate saturation, since carbonate precipitation is only the consequence, but not the cause of oversaturation. First results show that the saturation state is increased in the zone of phototrophic CO2 uptake. In contrast, the saturation state is strongly decreased in the zone where dissolved oxygen overlaps with dissolved sulphide. Aerobic sulphide oxidation consumes most of the HS- and dissipates most of the alkalinity produced in the sulphate reduction zone below. Hence, our results are consistent with the findings of Aloisi (2008), and they even more clearly show that sulphate reduction does not induce carbonate precipitation nor contributes to carbonate precipitation in combination with phototrophic CO2 uptake. The alkalinity effect of sulphate

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

    NASA Technical Reports Server (NTRS)

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

    1997-01-01

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

  12. Evaluation of the performance and applications of a metal hydride hydrogen compressor

    NASA Astrophysics Data System (ADS)

    Klausner, M.; McMillan, J.; Wickham, D.

    1984-09-01

    Low-grade energy from geothermal, solar or industrial process heat sources may be utilized to power a metal hydride compressor. A four-stage compressor, containing rare-earth metal alloys, compressed 35 standard liters per minute (SLPM) of hydrogen from 0.35 MPa (45 psia) to 3.5 MPa (480 psia), using 680 kg/h (3 GPM) of 80 C water. A computer model was written to simulate compressor performance. The application of the compressor in power cycles (Brayton gas cycles), and the economics of compressor operation were examined.

  13. Alkaline regenerative fuel cell systems for energy storage

    SciTech Connect

    Schubert, F.H.; Reid, M.A.; Martin, R.E.

    1981-01-01

    This paper presents the results of a preliminary design study of a Regenerative Fuel Cell Energy Storage system for application to future low-earth orbit space missions. This high energy density storage system is based on state-of-the-art alkaline electrolyte cell technology and incorporates dedicated fuel cell and electrolysis cell modules. 11 refs.

  14. 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/m3 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

  15. Metal-hydride energy-technological processing of hydrogen

    NASA Astrophysics Data System (ADS)

    Solovei, V. V.

    1983-03-01

    The external and internal irreversibility of the thermochemical hydrogen compression cycle is analyzed in relation to the efficiency of heat utilization in a metal-hydride energy system. The properties of the working fluid and the design of the metal-hydride elements are shown to have a considerable effect on the thermodynamic performance of a heat-utilizing installation for hydrogen processing.

  16. 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.

  17. Method of making crack-free zirconium hydride

    DOEpatents

    Sullivan, Richard W.

    1980-01-01

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

  18. Metal Hydrides for High-Temperature Power Generation

    SciTech Connect

    Ronnebro, Ewa; Whyatt, Greg A.; Powell, Michael R.; Westman, Matthew P.; Zheng, Feng; Fang, Zhigang Zak

    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, or 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/m3 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.

  19. 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.

  20. Flow injection on-line solid phase extraction for ultra-trace lead screening with hydride generation atomic fluorescence spectrometry.

    PubMed

    Wan, Zhuo; Xu, Zhangrun; Wang, Jianhua

    2006-01-01

    A flow injection (FI) on-line solid phase extraction (SPE) procedure for ultra-trace lead separation and preconcentration was developed, followed by hydride generation and atomic fluorescence spectrometric (AFS) detection. Lead is retained on an iminodiacetate chelating resin packed microcolumn, and is afterward eluted with 2.5% (v/v) hydrochloric acid to facilitate the hydride generation by reaction with alkaline tetrahydroborate solution with 1% (m/v) potassium ferricyanide as an oxidizing (or sensitizing) reagent. The hydride was separated from the reaction medium in the gas-liquid separator and swept into the atomizer for quantification. The chemical variables and the FI flow parameters were carefully optimized. With a sample loading volume of 4.8 ml, quantitative retention of lead was obtained, along with an enrichment factor of 11.3 and a sampling frequency of 50 h(-1). A detection limit of 4 ng l(-1), defined as 3 times the blank standard deviation (3 sigma), was achieved along with a RSD value of 1.6% at the 0.4 microg l(-1) level. The procedure was validated by determining lead contents in two certified reference materials, and its practical applicability was further demonstrated by analysing a variety of biological and environmental samples.

  1. Hydride morphology and striation formation during delayed hydride cracking in Zr-2.5% Nb

    NASA Astrophysics Data System (ADS)

    Shek, G. K.; Jovanoviċ, M. T.; Seahra, H.; Ma, Y.; Li, D.; Eadie, R. L.

    1996-08-01

    These experiments were designed to study hydride formation at the crack tip, acoustic emission (AE), potential drop (PD) and striation formation during DHC (delayed hydride cracking) in Zr-2.5% Nb. The test material was taken from an especially extrude pressure tube, which showed similar strength properties to normal pressure tube material but somewhat coarser microstructure. In testing at KI below 12 MPa √m at both 200 and 250°C very large striations (> 40 μ at 200 and >50 μm at 250°C) were produced. In simultaneous monitoring with acoustic emission and potential drop, both AE and PD jumps were shown to be monolithic. The number of striations on the fracture surface corresponded to the number of monolithic AE/PD jumps. Tapered shaped hydrides with the thick end adjacent to the crack tip were observed. These hydrides grew in size during the incubation period until they reached the striation length and then fractured monolithically. However, when KI was increased beyond about 12 MPa √m for these same specimens, the striation spacing decreased below 30 μ, the monolithic jumping dissolved into more continuous changes in signals, although the smaller striations were still visible on the fracture surface.

  2. ORNL Interim Progress Report on Hydride Reorientation CIRFT Tests

    SciTech Connect

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

    2016-10-28

    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 hydrides 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

  3. Electrochemical Studies on LaNi(sub 5-x)Sn(sub x) Metal Hydride Alloys

    NASA Technical Reports Server (NTRS)

    Ratnakumar, B. V.; Witham, C.; Bowman, R. C., Jr.; Hightower, A.; Fultz, B.

    1996-01-01

    Electrochemical studies were performed on LaNi(sub 5-x)Sn(sub x) with 0(less than or equal to)x(less than or equal to)0.5. We measured the effect of the Sn substituent on the kinetics of charge transfer and diffusion during hydrogen absorption and desorption, and the cyclic lifetimes of LaNi(sub 5-x)Sn(sub x) electrodes in 250 mAh laboratory test cells. We report beneficial effects of making small substitutions of Sn for Ni in LaNi(sub 5) on the performance of metal hydride alloy anode in terms of cyclic lifetime, capacity and kinetics. The optimal concentration of Sn in LaNi(sub 5-x)Sn(sub x) alloys for negative electrodes in alkaline rechargable secondary cells was found to lie in the range 0.25(less than or equal to)x(less than or equal to)0.3.

  4. Carbon cycling and snowball Earth.

    PubMed

    Goddéris, Yves; Donnadieu, Yannick

    2008-12-18

    The possibility that Earth witnessed episodes of global glaciation during the latest Precambrian challenges our understanding of the physical processes controlling the Earth's climate. Peltier et al. suggest that a 'hard snowball Earth' state may have been prevented owing to the release of CO(2) from the oxidation of dissolved organic carbon (DOC) in the ocean as the temperature decreased. Here we show that the model of Peltier et al. is not self-consistent as it implies large fluctuations of the ocean alkalinity content without providing any processes to account for it. Our findings suggest that the hard snowball Earth hypothesis is still valid.

  5. A novel plating process for microencapsulating metal hydrides

    SciTech Connect

    Law, H.H.; Vyas, B.; Zahurak, S.M.; Kammlott, G.W.

    1996-08-01

    One approach to increasing the lifetime of the metal hydride electrode has been the use of conventional electroless plating to produce a coating of copper or nickel on the surface of the metal hydride powders. In this paper, a novel method for microencapsulating the active electrode powders is presented. This new plating technique takes advantage of the reducing power of hydrogen already stored inside the metal hydride to plate a variety of metals onto metal hydride materials. This method greatly simplifies electroless plating for these powders, eliminating the need for stabilizers and additives typically required for conventional electroless plating solutions. Metals that can be electrolessly plated with stored hydrogen have been identified based on thermodynamic considerations. Experimentally, micrometers thick coatings of copper, silver, and nickel have been plated on several metal hydrides.

  6. 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.

  7. 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.

  8. Metal hydrides for concentrating solar thermal power energy storage

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  9. Recent advances in metal hydrides for clean energy applications

    SciTech Connect

    Ronnebro, Ewa; Majzoub, Eric H.

    2013-06-01

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

  10. Helium trapping at erbium oxide precipitates in erbium hydride

    SciTech Connect

    Foiles, Stephen M.; Battaile, Corbett Chandler

    2016-02-01

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

  11. Results of NDE Technique Evaluation of Clad Hydrides

    SciTech Connect

    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 to detect and characterize the hydrides, the potential exists to significantly increase test sample coverage while reducing evaluation time and cost. To demonstrate the viability this approach, an initial evaluation of eddy current and ultrasonic techniques were performed to demonstrate the basic ability to these techniques to detect hydrides or their effects on the microstructure. Conventional continuous wave eddy current techniques were applied to zirconium based cladding test samples thermally processed with hydrogen gas to promote the absorption of hydrogen and subsequent formation of hydrides. The results of the evaluation demonstrate that eddy current inspection approaches have the potential to detect both the physical damage induced by hydrides, e.g. blisters and cracking, as well as the combined effects of absorbed hydrogen and hydride precipitates on the electrical properties of the zirconium alloy. Similarly, measurements of ultrasonic wave velocities indicate changes in the elastic properties resulting from the combined effects of absorbed hydrogen and hydride precipitates as well as changes in geometry in regions of severe degradation. However, for both approaches, the signal responses intended to make the desired measurement incorporate a number of contributing

  12. Highly Concentrated Palladium Hydrides/Deuterides; Theory

    SciTech Connect

    Papaconstantopoulos, Dimitrios

    2013-11-26

    Accomplishments are reported in these areas: tight-binding molecular dynamics study of palladium; First-principles calculations and tight-binding molecular dynamics simulations of the palladium-hydrogen system; tight-binding studies of bulk properties and hydrogen vacancies in KBH{sub 4}; tight-binding study of boron structures; development of angular dependent potentials for Pd-H; and density functional and tight-binding calculations for the light-hydrides NaAlH4 and NaBH4

  13. Lithium hydride - A space age shielding material

    NASA Technical Reports Server (NTRS)

    Welch, F. H.

    1974-01-01

    Men and materials performing in the environment of an operating nuclear reactor require shielding from the escaping neutron particles and gamma rays. For efficient shielding from gamma rays, dense, high atomic number elements such as iron, lead, or tungsten are required, whereas light, low atomic number elements such as hydrogen, lithium, or beryllium are required for efficient neutron shielding. The use of lithium hydride (LiH) as a highly efficient neutron-shielding material is considered. It contains, combined into a single, stable compound, two of the elements most effective in attenuating and absorbing neutrons.

  14. Metal hydride fuel storage and method thereof

    DOEpatents

    Morse, Jeffrey D.; Jankowski, Alan F.; Yu, Conrad

    2010-08-10

    An apparatus having a first substrate having (1) a cavity, (2) one or more resistive heaters, and (3) one or more coatings forming a diffusion barrier to hydrogen; a second substrate having (1) an outlet valve comprising a pressure relief structure and (2) one or more coatings forming a diffusion barrier to hydrogen, wherein said second substrate is coupled to said first substrate forming a sealed volume in said cavity; a metal hydride material contained within said cavity; and a gas distribution system formed by coupling a microfluidic interconnect to said pressure relief structure. Additional apparatuses and methods are also disclosed.

  15. Development of nickel-metal hydride cell

    NASA Technical Reports Server (NTRS)

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

    1993-01-01

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

  16. Pressure-stabilized superconductive yttrium hydrides

    NASA Astrophysics Data System (ADS)

    Li, Yinwei; Hao, Jian; Liu, Hanyu; Tse, John S.; Wang, Yanchao; Ma, Yanming

    2015-05-01

    The search for high-temperature superconductors has been focused on compounds containing a large fraction of hydrogen, such as SiH4(H2)2, CaH6 and KH6. Through a systematic investigation of yttrium hydrides at different hydrogen contents using an structure prediction method based on the particle swarm optimization algorithm, we have predicted two new yttrium hydrides (YH4 andYH6), which are stable above 110 GPa. Three types of hydrogen species with increased H contents were found, monatomic H in YH3, monatomic H+molecular “H2” in YH4 and hexagonal “H6” unit in YH6. Interestingly, H atoms in YH6 form sodalite-like cage sublattice with centered Y atom. Electron-phonon calculations revealed the superconductive potential of YH4 and YH6 with estimated transition temperatures (Tc) of 84-95 K and 251-264 K at 120 GPa, respectively. These values are higher than the predicted maximal Tc of 40 K in YH3.

  17. Pressure-stabilized superconductive yttrium hydrides.

    PubMed

    Li, Yinwei; Hao, Jian; Liu, Hanyu; Tse, John S; Wang, Yanchao; Ma, Yanming

    2015-05-05

    The search for high-temperature superconductors has been focused on compounds containing a large fraction of hydrogen, such as SiH4(H2)2, CaH6 and KH6. Through a systematic investigation of yttrium hydrides at different hydrogen contents using an structure prediction method based on the particle swarm optimization algorithm, we have predicted two new yttrium hydrides (YH4 andYH6), which are stable above 110 GPa. Three types of hydrogen species with increased H contents were found, monatomic H in YH3, monatomic H+molecular "H2" in YH4 and hexagonal "H6" unit in YH6. Interestingly, H atoms in YH6 form sodalite-like cage sublattice with centered Y atom. Electron-phonon calculations revealed the superconductive potential of YH4 and YH6 with estimated transition temperatures (Tc) of 84-95 K and 251-264 K at 120 GPa, respectively. These values are higher than the predicted maximal Tc of 40 K in YH3.

  18. Pressure-stabilized superconductive yttrium hydrides

    PubMed Central

    Li, Yinwei; Hao, Jian; Liu, Hanyu; Tse, John S.; Wang, Yanchao; Ma, Yanming

    2015-01-01

    The search for high-temperature superconductors has been focused on compounds containing a large fraction of hydrogen, such as SiH4(H2)2, CaH6 and KH6. Through a systematic investigation of yttrium hydrides at different hydrogen contents using an structure prediction method based on the particle swarm optimization algorithm, we have predicted two new yttrium hydrides (YH4 andYH6), which are stable above 110 GPa. Three types of hydrogen species with increased H contents were found, monatomic H in YH3, monatomic H+molecular “H2” in YH4 and hexagonal “H6” unit in YH6. Interestingly, H atoms in YH6 form sodalite-like cage sublattice with centered Y atom. Electron-phonon calculations revealed the superconductive potential of YH4 and YH6 with estimated transition temperatures (Tc) of 84–95 K and 251–264 K at 120 GPa, respectively. These values are higher than the predicted maximal Tc of 40 K in YH3. PMID:25942452

  19. Metal hydrides for lithium-ion batteries.

    PubMed

    Oumellal, Y; Rougier, A; Nazri, G A; Tarascon, J-M; Aymard, L

    2008-11-01

    Classical electrodes for Li-ion technology operate via an insertion/de-insertion process. Recently, conversion electrodes have shown the capability of greater capacity, but have so far suffered from a marked hysteresis in voltage between charge and discharge, leading to poor energy efficiency and voltages. Here, we present the electrochemical reactivity of MgH(2) with Li that constitutes the first use of a metal-hydride electrode for Li-ion batteries. The MgH(2) electrode shows a large, reversible capacity of 1,480 mAh g(-1) at an average voltage of 0.5 V versus Li(+)/Li(o) which is suitable for the negative electrode. In addition, it shows the lowest polarization for conversion electrodes. The electrochemical reaction results in formation of a composite containing Mg embedded in a LiH matrix, which on charging converts back to MgH(2). Furthermore, the reaction is not specific to MgH(2), as other metal or intermetallic hydrides show similar reactivity towards Li. Equally promising, the reaction produces nanosized Mg and MgH(2), which show enhanced hydrogen sorption/desorption kinetics. We hope that such findings can pave the way for designing nanoscale active metal elements with applications in hydrogen storage and lithium-ion batteries.

  20. Regeneration of Aluminum Hydride Using Trimethylamine

    SciTech Connect

    D Lacina; J Reilly; Y Celebi; J Wegrzyn; J Johnson; J Graetz

    2011-12-31

    Aluminum hydride is an attractive reducing agent and energy storage compound possessing a low decomposition temperature and a high gravimetric and volumetric hydrogen density. However, it is thermodynamically unstable at room temperature and requires extremely high pressures to form the hydride from aluminum and hydrogen gas. Here, we describe an alternate method of synthesizing AlH{sub 3} using Ti-catalyzed Al powder, H{sub 2}, and trimethylamine (TMA) to form an alane adduct. The formation of trimethylamine alane occurs at modest hydrogen pressures ({approx}100 bar), forming the 2:1 bis complex (2 trimethylamine/AlH{sub 3}). Along with the hydrogenation product, mono (1:1) and bis (2:1) standards of TMA-AlH{sub 3} were prepared and characterized using X-ray diffraction and Raman spectroscopy. X-ray absorption spectroscopy of the reaction products showed that the Ti catalyst remains with the unreacted Al powder after hydrogenation and is not present in the alane adduct. We also demonstrate that TMA can be transaminated with triethylamine to form triethylamine alane, which can easily be separated to recover AlH{sub 3}.

  1. The development of metal hydrides using as concentrating solar thermal storage materials

    NASA Astrophysics Data System (ADS)

    Qu, Xuanhui; Li, Yang; Li, Ping; Wan, Qi; Zhai, Fuqiang

    2015-12-01

    Metal hydrides high temperature thermal heat storage technique has great promising future prospects in solar power generation, industrial waste heat utilization and peak load regulating of power system. This article introduces basic principle of metal hydrides for thermal storage, and summarizes developments in advanced metal hydrides high-temperature thermal storage materials, numerical simulation and thermodynamic calculation in thermal storage systems, and metal hydrides thermal storage prototypes. Finally, the future metal hydrides high temperature thermal heat storage technique is been looked ahead.

  2. 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

  3. Synthesis and hydride transfer reactions of cobalt and nickel hydride complexes to BX3 compounds.

    PubMed

    Mock, Michael T; Potter, Robert G; O'Hagan, Molly J; Camaioni, Donald M; Dougherty, William G; Kassel, W Scott; DuBois, Daniel L

    2011-12-05

    Hydrides of numerous transition metal complexes can be generated by the heterolytic cleavage of H(2) gas such that they offer alternatives to using main group hydrides in the regeneration of ammonia borane, a compound that has been intensely studied for hydrogen storage applications. Previously, we reported that HRh(dmpe)(2) (dmpe = 1,2-bis(dimethylphosphinoethane)) was capable of reducing a variety of BX(3) compounds having a hydride affinity (HA) greater than or equal to the HA of BEt(3). This study examines the reactivity of less expensive cobalt and nickel hydride complexes, HCo(dmpe)(2) and [HNi(dmpe)(2)](+), to form B-H bonds. The hydride donor abilities (ΔG(H(-))°) of HCo(dmpe)(2) and [HNi(dmpe)(2)](+) were positioned on a previously established scale in acetonitrile that is cross-referenced with calculated HAs of BX(3) compounds. The collective data guided our selection of BX(3) compounds to investigate and aided our analysis of factors that determine favorability of hydride transfer. HCo(dmpe)(2) was observed to transfer H(-) to BX(3) compounds with X = H, OC(6)F(5), and SPh. The reaction with B(SPh)(3) is accompanied by the formation of dmpe-(BH(3))(2) and dmpe-(BH(2)(SPh))(2) products that follow from a reduction of multiple B-SPh bonds and a loss of dmpe ligands from cobalt. Reactions between HCo(dmpe)(2) and B(SPh)(3) in the presence of triethylamine result in the formation of Et(3)N-BH(2)SPh and Et(3)N-BH(3) with no loss of a dmpe ligand. Reactions of the cationic complex [HNi(dmpe)(2)](+) with B(SPh)(3) under analogous conditions give Et(3)N-BH(2)SPh as the final product along with the nickel-thiolate complex [Ni(dmpe)(2)(SPh)](+). The synthesis and characterization of HCo(dedpe)(2) (dedpe = Et(2)PCH(2)CH(2)PPh(2)) from H(2) and a base is also discussed, including the formation of an uncommon trans dihydride species, trans-[(H)(2)Co(dedpe)(2)][BF(4)].

  4. Synthesis and Hydride Transfer Reactions of Cobalt and Nickel Hydride Complexes to BX₃ Compounds

    SciTech Connect

    Mock, Michael T.; Potter, Robert G.; O'Hagan, Molly; Camaioni, Donald M.; Dougherty, William G.; Kassel, W. Scott; DuBois, Daniel L.

    2011-10-31

    Hydrides of numerous transition metal complexes can be generated by the heterolytic cleavage of H₂ gas such that they offer alternatives to using main group hydrides in the regeneration of ammonia borane, a compound that has been intensely studied for hydrogen storage applications. Previously, we reported that HRh(dmpe)₂ (dmpe = 1,2-bis(dimethylphosphinoethane)) was capable of reducing a variety of BX₃ compounds having a hydride affinity (HA) greater than or equal to the HA of BEt₃. This study examines the reactivity of less expensive cobalt and nickel hydride complexes, HCo(dmpe)₂ and [HNi(dmpe)₂]+, to form B–H bonds. The hydride donor abilities (ΔGH °) of HCo(dmpe)₂ and [HNi(dmpe)₂]+ were positioned on a previously established scale in acetonitrile that is cross-referenced with calculated HAs of BX₃ compounds. The collective data guided our selection of BX₃ compounds to investigate and aided our analysis of factors that determine favorability of hydride transfer. HCo(dmpe)₂ was observed to transfer H to BX₃ compounds with X = H, OC₆F₅, and SPh. The reaction with B(SPh)₃ is accompanied by the formation of dmpe-(BH₃)₂ and dmpe-(BH₂(SPh))₂ products that follow from a reduction of multiple B–SPh bonds and a loss of dmpe ligands from cobalt. Reactions between HCo(dmpe)₂ and B(SPh)₃ in the presence of triethylamine result in the formation of Et₃N–BH₂SPh and Et₃N–BH₃ with no loss of a dmpe ligand. Reactions of the cationic complex [HNi(dmpe)₂]+ with B(SPh)₃ under analogous conditions give Et₃N–BH₂SPh as the final product along with the nickel–thiolate complex [Ni(dmpe)₂(SPh)]+. The synthesis and characterization of HCo(dedpe)₂ (dedpe = Et₂PCH₂CH₂PPh₂) from H₂ and a base is also discussed, including the formation of an uncommon trans dihydride species, trans-[(H)₂Co(dedpe)₂][BF₄].

  5. Synthesis and Hydride Transfer Reactions of Cobalt and Nickel Hydride Complexes to BX3 Compounds

    SciTech Connect

    Mock, Michael T.; Potter, Robert G.; O'Hagan, Molly J.; Camaioni, Donald M.; Dougherty, William G.; Kassel, W. S.; DuBois, Daniel L.

    2011-12-05

    Hydrides of numerous transition metal complexes can be generated by the heterolytic cleavage of H{sub 2} gas such that they offer alternatives to using main group hydrides in the regeneration of ammonia borane, a compound that has been intensely studied for hydrogen storage applications. Previously, we reported that HRh(dmpe){sub 2}, dmpe = 1,2-bis(dimethylphosphinoethane) was capable of reducing a variety of BX{sub 3} compounds having hydride affinity (HA) greater than or equal to HA of BEt{sub 3}. This study examines the reactivity of less expensive cobalt and nickel hydride complexes, (HCo(dmpe){sub 2} and [HNi(dmpe){sub 2}]{sup +}), to form B-H bonds. The hydride donor abilities ({Delta}G{sub H{sup -}}{sup o}) of HCo(dmpe){sub 2} and [HNi(dmpe){sub 2}]{sup +} were positioned on a previously established scale in acetonitrile that is cross-referenced with calculated HAs of BX{sub 3} compounds. The collective data guided our selection of BX{sub 3} compounds to investigate and aided our analysis of factors that determine favorability of hydride transfer. HCo(dmpe){sub 2} was observed to transfer H{sup -} to BX{sub 3} compounds with X = H, OC{sub 6}F{sub 5} and SPh. The reaction with B(SPh){sub 3} is accompanied by formation of (BH{sub 3}){sub 2}-dmpe and (BH{sub 2}SPh){sub 2}-dmpe products that follow from reduction of multiple BSPh bonds and loss of a dmpe ligand from Co. Reactions between HCo(dmpe){sub 2} and B(SPh){sub 3} in the presence of triethylamine result in formation of Et{sub 3}N-BH{sub 2}SPh and Et{sub 3}N-BH{sub 3} with no loss of dmpe ligand. Reactions of the cationic complex [HNi(dmpe){sub 2}]{sup +} with B(SPh){sub 3} under analogous conditions give Et{sub 3}N-BH{sub 2}SPh as the final product along with the nickel-thiolate complex [Ni(dmpe){sub 2}(SPh)]{sup +}. The synthesis and characterization of HCo(dedpe){sub 2} (dedpe = diethyldiphenyl(phosphino)ethane) from H{sub 2} and a base is also discussed; including the formation of an uncommon trans

  6. Hot temperatures line lists for metal hydrides

    NASA Astrophysics Data System (ADS)

    Gorman, M.; Lodi, L.; Leyland, P. pC; Hill, C.; Yurchenko, S. N.; Tennyson, J.

    2013-09-01

    The ExoMol project is an ERC funded project set up with the purpose of calculating high quality theoretical molecular line list data to facilitate the emerging field of exoplanet and cool star atmospheric haracterisation [1]. Metal hydrides are important building blocks of interstellar physical chemistry. For molecular identification and characterisation in astrophysical sources, one requires accurate and complete spectroscopic data including transitional frequencies and intensities in the form of a line list. The ab initio methods offer the best opportunity for detailed theoretical studies of free diatomic metal hydrides and other simple hydride molecules. In this contribution we present progress on theoretical line lists for AlH, CrH, MgH, NiH, NaH and TiH obtained from first principles, applicable for a large range of temperatures up to 3500 K. Among the hydrides, AlH is of special interest because of a relatively high cosmic abundance of aluminium. The presence of AlH has been detected in the spectra of M-type and S-type stars as well as in sunspots (See [2] and references therein). CrH is a molecule of astrophysical interest; under the classification scheme developed by Kirkpatrick et al [3], CrH is of importance in distinguishing L type brown dwarfs. It has been proposed that theoretical line-lists of CrH and CrD could be used to facilitate a 'Deuterium test' for use in distinguishing planets, brown dwarfs and stars [5] and also it has been speculated that CrH exists in sunspots [4] but a higherquality hot-temperature line-list is needed to confirm this finding. The presence of MgH in stellar spectra is well documented through observation of the A2 ! X 2+ and B0 2+ ! X 2+ transitions. Different spectral features of MgH have been used as an indicator for the magnesium isotope abundances in the atmospheres of different stars from giants to dwarfs including the Sun, to measure the temperature of stars, surface gravity, stars' metal abundance, gravitational, as

  7. Synthesis and some reactions of dibutyltin (S)- and (R)-camphorsulfonyl hydrides.

    PubMed

    Kinart, Wojciech J; Kinart, Cezary M; Kozak, Monika; Kinart, Andrzej; Sendecki, Marcin; Matczak, Piotr

    2009-08-01

    The synthesis and physical properties of dibutyltin (S)-camphorsulfonyl hydride (1) and dibutyltin (R)-camphorsulfonyl hydride (2), and diphenyltin (S)-camphorsulfonyl hydride (3) as well as that of their organotin precursors are described. Their reactivity with different amines as triethylamine, morpholine and pyridine has been compared with other mixed hydrides as dibutyltin chloride hydride, dibutyltin acetate hydride and dibutyltin dihydride. It has been studied also the possibility of using of dibutyltin (R)- or (S)-camphorsulfonyl hydrides for the stereoselective reduction of different ketones as acetophenone, menthon, camphor and cyclopropyl-(4-metoxyphenyl)-methanone. The reduction of acetophenone with studied camphorsulfonyl hydrides carried out in benzene at room temperature afforded 1-phenylethanol with relatively low enantioselectivity. Addition of 10 equiv. of MnCl(2)*4H(2)O or ZnCl(2) to the reduction mixture involving dibutyltin (S)-camphorsulfonyl hydride (1) and acetophenone and carried out in methanol and tetrahydrofuran, respectively, resulted in remarkable increase in enantioselectivity. The comparative kinetic studies of reduction of acetophenone by different hydrides proved that dibutyltin camphorsulfonyl hydride is significantly more reactive in comparison with dibutyltin chloro hydride and dibutyltin acetate hydride. Analogous results have been obtained from kinetic studies for different tin hydrides with chosen amines. The outcome of these studies supported by theoretical calculations led to the conclusion that the order of reactivity of the studied hydrides correlates with the rate of their homolytic decomposition at room temperature.

  8. Advanced technology for extended endurance alkaline fuel cells

    NASA Astrophysics Data System (ADS)

    Sheibley, D. W.; Martin, R. A.

    Advanced components have been developed for alkaline fuel cells with a view to the satisfaction of NASA Space Station design requirements for extended endurance. The components include a platinum-on-carbon catalyst anode, a potassium titanate-bonded electrolyte matrix, a lightweight graphite electrolyte reservoir plate, a gold-plated nickel-perforated foil electrode substrate, a polyphenylene sulfide cell edge frame material, and a nonmagnesium cooler concept. When incorporated into the alkaline fuel cell unit, these components are expected to yield regenerative operation in a low earth orbit Space Station with a design life greater than 5 years.

  9. Advanced technology for extended endurance alkaline fuel cells

    NASA Technical Reports Server (NTRS)

    Sheibley, D. W.; Martin, R. A.

    1987-01-01

    Advanced components have been developed for alkaline fuel cells with a view to the satisfaction of NASA Space Station design requirements for extended endurance. The components include a platinum-on-carbon catalyst anode, a potassium titanate-bonded electrolyte matrix, a lightweight graphite electrolyte reservoir plate, a gold-plated nickel-perforated foil electrode substrate, a polyphenylene sulfide cell edge frame material, and a nonmagnesium cooler concept. When incorporated into the alkaline fuel cell unit, these components are expected to yield regenerative operation in a low earth orbit Space Station with a design life greater than 5 years.

  10. 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.

  11. 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

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

    DTIC Science & Technology

    2016-01-04

    a solid with six crystalline phases. In principle, alane is a promising propellant . The specific impulse of an AP/HTPB propellant mixed with alane...Distribution approved for public release. 2     Introduction Boranes (boron hydrides) were once thought to be promising propellants .1-14 The reasons...diborane, hydrogen, and a white solid . Whatley et al.8 studied the products of diborane oxidation. Roth and co-workers9 found HOBO to be the main

  13. ENVIRONMENTAL REACTIVITY OF SOLID STATE HYDRIDE MATERIALS

    SciTech Connect

    Gray, J; Donald Anton, D

    2009-04-23

    In searching for high gravimetric and volumetric density hydrogen storage systems, it is inevitable that higher energy density materials will be used. In order to make safe and commercially acceptable condensed phase hydrogen storage systems, it is important to understand quantitatively the risks involved in using and handling these materials and to develop appropriate mitigation strategies to handle potential material exposure events. A crucial aspect of the development of risk identification and mitigation strategies is the development of rigorous environmental reactivity testing standards and procedures. This will allow for the identification of potential risks and implementation of risk mitigation strategies. Modified testing procedures for shipping air and/or water sensitive materials, as codified by the United Nations, have been used to evaluate two potential hydrogen storage materials, 2LiBH{sub 4} {center_dot} MgH{sub 2} and NH{sub 3}BH{sub 3}. The modified U.N. procedures include identification of self-reactive substances, pyrophoric substances, and gas-emitting substances with water contact. The results of these tests for air and water contact sensitivity will be compared to the pure material components where appropriate (e.g. LiBH{sub 4} and MgH{sub 2}). The water contact tests are divided into two scenarios dependent on the hydride to water mole ratio and heat transport characteristics. Air contact tests were run to determine whether a substance will spontaneously react with air in a packed or dispersed form. In the case of the 2LiBH{sub 4} {center_dot} MgH{sub 2} material, the results from the hydride mixture compared to the pure materials results showed the MgH{sub 2} to be the least reactive component and LiBH{sub 4} the more reactive. The combined 2LiBH{sub 4} {center_dot} MgH{sub 2} resulted in a material having environmental reactivity between these two materials. Relative to 2LiBH{sub 4} {center_dot} MgH{sub 2}, the chemical hydride NH{sub 3}BH

  14. Relativistic effects on sixth group hydrides

    NASA Astrophysics Data System (ADS)

    Pisani, L.; Clementi, E.

    1994-08-01

    Dirac-Fock (DF) and Hartree-Fock (HF) calculations have been performed for the ground state configuration of the H2O, H2S, H2Se, H2Te, and H2Po molecules. Equilibrium geometries, atomization energies, and molecular orbitals energies are evaluated with both methods, compared and discussed with the help of population analysis and atomic orbital energies. Particular attention has been given to a qualitative understanding of the relativistic effects. Molecular spin-orbits corrections appear to be essential to a description of some in the sixth group hydrides set. A description of the relativistic computer program is presented elsewhere [L. Pisani and E. Clementi, J. Comput. Chem. (in press)].

  15. Zirconium Hydride Space Power Reactor design.

    NASA Technical Reports Server (NTRS)

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

    1972-01-01

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

  16. Far-infrared spectrum of sodium hydride

    NASA Astrophysics Data System (ADS)

    Leopold, K. R.; Zink, L. R.; Evenson, K. M.; Jennings, D. A.

    1987-03-01

    Rotational spectra in the v = 0, 1, 2, and 3 levels of the ground ( 1Σ) state of sodium hydride have been observed using tunable far-infrared radiation generated from the difference frequency between two CO 2 lasers. The Dunham coefficients, which have been determined without the use of optical data or isotopic scaling relations, are Y01 = 146 999.138(38) MHz, Y02 = -10.29481(54) MHz, Y03 = 6.243(49) × 10 -4 MHz, Y11 = -4109.912(68) MHz, Y12 = 0.14695(68) MHz, Y21 = 33.341(34) MHz, Y22 = -2.69(20) × 10 -3 MHz, and Y31 = -1.0517(55) MHz. The constants are typically an order of magnitude more accurate than the best values previously available, and where comparison is possible, agreement is found to be excellent.

  17. Process for production of a metal hydride

    SciTech Connect

    Allen, Nathan Tait; Butterick, III, Robert; Chin, Arthur Achhing; Millar, Dean Michael; Molzahn, David Craig

    2014-08-12

    A process for production of a metal hydride compound MH.sub.x, wherein x is one or two and M is an alkali metal, Be or Mg. The process comprises combining a compound of formula (R.sup.1O).sub.xM with aluminum, hydrogen and at least one metal selected from among titanium, zirconium, hafnium, niobium, vanadium, tantalum and iron to produce a compound of formula MH.sub.x. R.sup.1 is phenyl or phenyl substituted by at least one alkyl or alkoxy group. A mole ratio of aluminum to (R.sup.1O).sub.xM is from 0.1:1 to 1:1. The catalyst is present at a level of at least 200 ppm based on weight of aluminum.

  18. 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.

  19. Thermally unstable hydrides of titanium aluminide Ti3Al

    NASA Astrophysics Data System (ADS)

    Kazantseva, N. V.; Popov, A. G.; Mushnikov, N. V.; Skripov, A. V.; Soloninin, A. V.; Aleksashin, B. A.; Novozhenov, V. I.; Sazonova, V. A.; Kharisova, A. G.

    2011-04-01

    The hydrogen capacity of (Ti, Nb)3Al titanium aluminides subjected to mechanical activation in a hydrogen atmosphere has been studied. It has been shown that the application of this procedure allows one to prepare thermally unstable titanium aluminide (Ti3Al) hydrides with a high hydrogen content (to 2.6 wt %) at room temperature and normal pressure; in this case, no special requirements for the hydrogen purity are placed. The thermally unstable nanostructured Ti3Al hydrides were found to exhibit a higher hydrogen mobility as compared to that of the microcrystalline hydrides. Low niobium additions (to 2.1 at %) have been found to decrease the hydrogen capacity. Experiments on the preparation of bulk samples from the hydride powders obtained were performed.

  20. Life test results of hydride compressors for cryogenic refrigerators

    NASA Astrophysics Data System (ADS)

    Jones, J. A.; Golben, P. M.

    1984-01-01

    A development status assessment is made, from the viewpoint of system durability, for the hydride compressors used in such cryogenic refrigerators as that of the JPL, which has operated at 29 K for 500 hours and at lower temperatures for over 1000. Attention is given to a novel hydride compressor unit which has operated through 35,000 cycles and exhibits negligible degradation of check valves, hydride particle size, and expansion valves. The power requirement for liquid hydrogen cooling can be halved through the use of recuperative hot water heating methods, making this system comparable in power use to liquid hydrogen refrigeration systems operating on electricity. Due to the lack of moving parts in hydride refrigerator designs, potential service lifetimes of many years, and perhaps decades, are being projected.

  1. High-pressure synthesis of noble metal hydrides

    NASA Astrophysics Data System (ADS)

    Donnerer, Christian; Scheler, Thomas; Gregoryanz, Eugene

    2013-04-01

    The formation of hydride phases in the noble metals copper, silver, and gold was investigated by in situ x-ray diffraction at high hydrogen pressures. In the case of copper, a novel hexagonal hydride phase, Cu2H, was synthesised at pressures above 18.6 GPa. This compound exhibits an anti-CdI2-type structure, where hydrogen atoms occupy every second layer of octahedral interstitial sites. In contrast to chemically produced CuH, this phase does not show a change in compressibility compared to pure copper. Furthermore, repeated compression (after decomposition of Cu2H) led to the formation of cubic copper hydride at 12.5 GPa, a phenomenon attributed to an alteration of the microstructure during dehydrogenation. No hydrides of silver (up to 87 GPa) or gold (up to 113 GPa) were found at both room and high temperatures.

  2. The development of lightweight hydride alloys based on magnesium

    SciTech Connect

    Guthrie, S.E.; Thomas, G.J.; Yang, N.Y.C.; Bauer, W.

    1996-02-01

    The development of a magnesium based hydride material is explored for use as a lightweight hydrogen storage medium. It is found that the vapor transport of magnesium during hydrogen uptake greatly influences the surface and hydride reactions in these alloys. This is exploited by purposely forming near-surface phases of Mg{sub 2}Ni on bulk Mg-Al-Zn alloys which result in improved hydrogen adsorption and desorption behavior. Conditions were found where these near-surface reactions yielded a complex and heterogeneous microstructure that coincided with excellent bulk hydride behavior. A Mg-Al alloy hydride is reported with near atmospheric plateau pressures at temperatures below 200{degrees}C. Additionally, a scheme is described for low temperature in-situ fabrication of Mg{sub 2}Ni single phase alloys utilizing the high vapor pressure of Mg.

  3. 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)

  4. Artificial exomuscle investigations for applications--metal hydride.

    PubMed

    Crevier, Marie-Charlotte; Richard, Martin; Rittenhouse, D Matheson; Roy, Pierre-Olivier; Bédard, Stéphane

    2007-03-01

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

  5. High-pressure synthesis of noble metal hydrides.

    PubMed

    Donnerer, Christian; Scheler, Thomas; Gregoryanz, Eugene

    2013-04-07

    The formation of hydride phases in the noble metals copper, silver, and gold was investigated by in situ x-ray diffraction at high hydrogen pressures. In the case of copper, a novel hexagonal hydride phase, Cu2H, was synthesised at pressures above 18.6 GPa. This compound exhibits an anti-CdI2-type structure, where hydrogen atoms occupy every second layer of octahedral interstitial sites. In contrast to chemically produced CuH, this phase does not show a change in compressibility compared to pure copper. Furthermore, repeated compression (after decomposition of Cu2H) led to the formation of cubic copper hydride at 12.5 GPa, a phenomenon attributed to an alteration of the microstructure during dehydrogenation. No hydrides of silver (up to 87 GPa) or gold (up to 113 GPa) were found at both room and high temperatures.

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

    SciTech Connect

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

    2013-01-01

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

  7. 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)

  8. Hydrogen storage in sodium aluminum hydride.

    SciTech Connect

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

    2005-11-01

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

  9. Mesozoic mafic alkaline magmatism of southern Scandinavia

    NASA Astrophysics Data System (ADS)

    Tappe, Sebastian

    2004-11-01

    More than 100 volcanic necks in central Scania (southern Sweden) are the product of Jurassic continental rift-related mafic alkaline magmatism at the southwest margin of the Baltic Shield. They are mainly basanites, with rarer melanephelinites. Both rock groups display overlapping primitive Mg-numbers, Cr and Ni contents, steep chondrite-normalized rare earth element patterns (LaN /YbN = 17 27) and an overall enrichment in incompatible elements. However, the melanephelinites are more alkaline and have stronger high field strength element enrichment than the basanites. The existence of distinct primary magmas is also indicated by heterogeneity in highly incompatible element ratios (e.g. Zr/Nb, La/Nb). Trace element modelling indicates that the magmas were generated by comparably low degrees of melting of a heterogeneous mantle source. Such a source can best be explained by a metasomatic overprint of the mantle lithosphere by percolating evolved melts. The former existence of such alkaline trace element-enriched melts can be demonstrated by inversion of the trace element content of green-core clinopyroxenes and anorthoclase which occur as xenocrysts in the melanephelinites and are interpreted as being derived from crystallization of evolved mantle melts. Jurassic magmatic activity in Scania was coeval with the generation of nephelinites in the nearby Egersund Basin (Norwegian North Sea). Both Scanian and North Sea alkaline magmas share similar trace element characteristics. Mantle enrichment processes at the southwest margin of the Baltic Shield and the North Sea Basin generated trace element signatures similar to those of ocean island basalts (e.g. low Zr/Nb and La/Nb) but there are no indications of plume activity during the Mesozoic in this area. On the contrary, the short duration of rifting, absence of extensive lithospheric thinning, and low magma volumes argue against a Mesozoic mantle plume. It seems likely that the metasomatic imprint resulted from the

  10. Ab-Initio Study of the Group 2 Hydride Anions

    NASA Astrophysics Data System (ADS)

    Harris, Joe P.; Wright, Timothy G.; Manship, Daniel R.

    2013-06-01

    The beryllium hydride (BeH)- dimer has recently been shown to be surprisingly strongly bound, with an electronic structure which is highly dependent on internuclear separation. At the equilibrium distance, the negative charge is to be found on the beryllium atom, despite the higher electronegativity of the hydrogen. The current study expands this investigation to the other Group 2 hydrides, and attempts to explain these effects. M. Verdicchio, G. L. Bendazzoli, S. Evangelisti, T. Leininger J. Phys. Chem. A, 117, 192, (2013)

  11. 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.

  12. Development of the Low-Pressure Hydride/Dehydride Process

    SciTech Connect

    Rueben L. Gutierrez

    2001-04-01

    The low-pressure hydride/dehydride process was developed from the need to recover thin-film coatings of plutonium metal from the inner walls of an isotope separation chamber located at Los Alamos and to improve the safety operation of a hydride recovery process using hydrogen at a pressure of 0.7 atm at Rocky Flats. This process is now the heart of the Advanced Recovery and Integrated Extraction System (ARIES) project.

  13. Alkaline battery, separator therefore

    NASA Technical Reports Server (NTRS)

    Schmidt, George F. (Inventor)

    1980-01-01

    An improved battery separator for alkaline battery cells has low resistance to electrolyte ion transfer and high resistance to electrode ion transfer. The separator is formed by applying an improved coating to an electrolyte absorber. The absorber, preferably, is a flexible, fibrous, and porous substrate that is resistant to strong alkali and oxidation. The coating composition includes an admixture of a polymeric binder, a hydrolyzable polymeric ester and inert fillers. The coating composition is substantially free of reactive fillers and plasticizers commonly employed as porosity promoting agents in separator coatings. When the separator is immersed in electrolyte, the polymeric ester of the film coating reacts with the electrolyte forming a salt and an alcohol. The alcohol goes into solution with the electrolyte while the salt imbibes electrolyte into the coating composition. When the salt is formed, it expands the polymeric chains of the binder to provide a film coating substantially permeable to electrolyte ion transfer but relatively impermeable to electrode ion transfer during use.

  14. Tellurium Hydrides at High Pressures: High-Temperature Superconductors

    NASA Astrophysics Data System (ADS)

    Zhong, Xin; Wang, Hui; Zhang, Jurong; Liu, Hanyu; Zhang, Shoutao; Song, Hai-Feng; Yang, Guochun; Zhang, Lijun; Ma, Yanming

    2016-02-01

    Observation of high-temperature superconductivity in compressed sulfur hydrides has generated an irresistible wave of searches for new hydrogen-containing superconductors. We herein report the prediction of high-Tc superconductivity in tellurium hydrides stabilized at megabar pressures identified by first-principles calculations in combination with a swarm structure search. Although tellurium is isoelectronic to sulfur or selenium, its heavier atomic mass and weaker electronegativity makes tellurium hydrides fundamentally distinct from sulfur or selenium hydrides in stoichiometries, structures, and chemical bondings. We identify three metallic stoichiometries of H4Te , H5Te2 , and HTe3 , which are not predicted or known stable structures for sulfur or selenium hydrides. The two hydrogen-rich H4Te and H5Te2 phases are primarily ionic and contain exotic quasimolecular H2 and linear H3 units, respectively. Their high-Tc (e.g., 104 K for H4Te at 170 GPa) superconductivity originates from the strong electron-phonon couplings associated with intermediate-frequency H-derived wagging and bending modes, a superconducting mechanism which differs substantially with those in sulfur or selenium hydrides where the high-frequency H-stretching vibrations make considerable contributions.

  15. Novel fuel cell stack with coupled metal hydride containers

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

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

    SciTech Connect

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

    2013-09-30

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

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

    NASA Astrophysics Data System (ADS)

    Li, Ruiwen; Wang, Xiaolin

    2014-06-01

    To study the behavior of hydrogen corrosion at the surface of U, U-2.5 wt%Nb alloy and U-5.7 wt%Nb, a gas-solid reaction system with an in situ microscope was designed. The nucleation and growth of the hydride of the alloy were continuously observed and recorded by a computer. The different characteristics of the hydrides on U metal and U-2.5 wt%Nb showed that the later alloy is more susceptible to hydrogen corrosion than the former. The growth rate of hydride of U-2.5 wt%Nb, calculated by measuring the perimeter of the hydride spots recorded by the in situ microscope, exhibited a reaction temperature dependency in the range of 40-160 °C, for pressure of 0.8 × 105 Pa. An Arrhenius plot for growth rate versus temperature yielded activation energy of 24.34 kJ/mol for the hydriding of U-2.5 wt%Nb alloy. The maximum hydriding rate was obtained at 125 °C, whose thermodynamics reason was discussed.

  18. Trialkylborane-Assisted CO(2) Reduction by Late Transition Metal Hydrides.

    PubMed

    Miller, Alexander J M; Labinger, Jay A; Bercaw, John E

    2011-01-01

    Trialkylborane additives promote reduction of CO(2) to formate by bis(diphosphine) Ni(II) and Rh(III) hydride complexes. The late transition metal hydrides, which can be formed from dihydrogen, transfer hydride to CO(2) to give a formate-borane adduct. The borane must be of appropriate Lewis acidity: weaker acids do not show significant hydride transfer enhancement, while stronger acids abstract hydride without CO(2) reduction. The mechanism likely involves a pre-equilibrium hydride transfer followed by formation of a stabilizing formate-borane adduct.

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

    PubMed Central

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

    2016-01-01

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

  20. Early Earth

    NASA Astrophysics Data System (ADS)

    Brown, M.

    2015-05-01

    Earth has continents, subduction and mobile lid plate tectonics, but details of the early evolution are poorly understood. Here I summarize the Hadean-Archean record, review evidence for a hotter Earth and consider geodynamic models for early Earth.

  1. Designing metal hydride complexes for water splitting reactions: a molecular electrostatic potential approach.

    PubMed

    Sandhya, K S; Suresh, Cherumuttathu H

    2014-08-28

    The hydridic character of octahedral metal hydride complexes of groups VI, VII and VIII has been systematically studied using molecular electrostatic potential (MESP) topography. The absolute minimum of MESP at the hydride ligand (Vmin) and the MESP value at the hydride nucleus (VH) are found to be very good measures of the hydridic character of the hydride ligand. The increasing/decreasing electron donating feature of the ligand environment is clearly reflected in the increasing/decreasing negative character of Vmin and VH. The formation of an outer sphere metal hydride-water complex showing the HH dihydrogen interaction is supported by the location and the value of Vmin near the hydride ligand. A higher negative MESP suggested lower activation energy for H2 elimination. Thus, MESP features provided a way to fine-tune the ligand environment of a metal-hydride complex to achieve high hydridicity for the hydride ligand. The applicability of an MESP based hydridic descriptor in designing water splitting reactions is tested for group VI metal hydride model complexes of tungsten.

  2. Chemical Hydride Slurry for Hydrogen Production and Storage

    SciTech Connect

    McClaine, Andrew W

    2008-09-30

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

  3. The Alkaline Dissolution Rate of Calcite.

    PubMed

    Colombani, Jean

    2016-07-07

    Due to the widespread presence of calcium carbonate on Earth, several geochemical systems, among which is the global CO2 cycle, are controlled to a large extent by the dissolution and precipitation of this mineral. For this reason, the dissolution of calcite has been thoroughly investigated for decades. Despite this intense activity, a consensual value of the dissolution rate of calcite has not been found yet. We show here that the inconsistency between the reported values stems mainly from the variability of the chemical and hydrodynamic conditions of measurement. The spreading of the values, when compared in identical conditions, is much less than expected and is interpreted in terms of sample surface topography. This analysis leads us to propose benchmark values of the alkaline dissolution rate of calcite compatible with all the published values, and a method to use them in various chemical and hydrodynamic contexts.

  4. Hydrogen Supply System for Small PEM Fuel Cell Stacks

    DTIC Science & Technology

    1997-07-01

    hydride to control the reaction rate and to control the heat release. Heat release is controlled by mixing alkaline or alkaline earth metal hydrides with...the boron or aluminum complex hydrides. These materials decompose endothermically .. .We used this effect to limit the heat release of hydrogen pellets...it renders the solid product reactive with water as lithium hydride is formed when the pellet is reacted. The reaction rates used by Beckert & Dengel

  5. Influence of uranium hydride oxidation on uranium metal behaviour

    SciTech Connect

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

    2013-07-01

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

  6. Spectrophotometric detection of arsenic using flow-injection hydride generation following sorbent extraction preconcentration.

    PubMed

    Neto, J A; Montes, R; Cardoso, A A

    1999-12-06

    An automated system with a C(18) bonded silica gel packed minicolumn is proposed for spectrophotometric detection of arsenic using flow-injection hydride generation following sorbent extraction preconcentration. Complexes formed between arsenic(III) and ammonium diethyl dithiophosphate (ADDP) are retained on a C(18) sorbent. The eluted As-DDP complexes are merged with a 1.5% (w/v) NaBH(4) and the resulting solution is thereafter injected into the hydride generator/gas-liquid separator. The arsine generated is carried out by a stream of N(2) and trapped in an alkaline iodine solution in which the analyte is determined by the arsenomolybdenum blue method. With preconcentration time of 120 s, calibration in the 5.00-50.0 mug As l(-1) range and sampling rate of about 20 samples h(-1) are achieved, corresponding to 36 mg ADDP plus 36 mg ammonium heptamolybdate plus 7 mg hydrazine sulfate plus 0.7 mg stannous chloride and about 7 ml sample consumed per determination. The detection limit is 0.06 mug l(-1) and the relative standard deviation (n=12) for a typical 17.0 mug As l(-1) sample is ca. 6%. The accuracy was checked for arsenic determination in plant materials from the NIST (1572 citrus leaves; 1573 tomato leaves) and the results were in agreement with the certified values at 95% confidence level. Good recoveries (94-104%) of spiked tap waters, sugars and synthetic mixtures of trivalent and pentavalent arsenic were also found.

  7. The alkaline and alkaline-carbonatite magmatism from Southern Brazil

    NASA Astrophysics Data System (ADS)

    Ruberti, E.; Gomes, C. D. B.; Comin-Chiaramonti, P.

    2015-12-01

    Early to Late Cretaceous lasting to Paleocene alkaline magmatism from southern Brazil is found associated with major extensional structural features in and around the Paraná Basin and grouped into various provinces on the basis of several data. Magmatism is variable in size, mode of occurrence and composition. The alkaline rocks are dominantly potassic, a few occurrences showing sodic affinity. The more abundant silicate rocks are evolved undersaturated to saturated in silica syenites, displaying large variation in igneous forms. Less evolved types are restricted to subvolcanic environments and outcrops of effusive suites occur rarely. Cumulatic mafic and ultramafic rock types are very common, particularly in the alkali-carbonatitic complexes. Carbonatite bodies are represented by Ca-carbonatites and Mg-carbonatites and more scarcely by Fe-carbonatites. Available radiometric ages for the alkaline rocks fit on three main chronological groups: around 130 Ma, subcoveal with the Early Cretaceous flood tholeiites of the Paraná Basin, 100-110 Ma and 80-90 Ma (Late Cretaceous). The alkaline magmatism also extends into Paleocene times, as indicated by ages from some volcanic lavas. Geochemically, alkaline potassic and sodic rock types are distinguished by their negative and positive Nb-Ta anomalies, respectively. Negative spikes in Nb-Ta are also a feature common to the associated tholeiitic rocks. Sr-Nd-Pb systematics confirm the contribution of both HIMU and EMI mantle components in the formation of the alkaline rocks. Notably, Early and Late Cretaceous carbonatites have the same isotopic Sr-Nd initial ratios of the associated alkaline rocks. C-O isotopic Sr-Nd isotopic ratios indicate typical mantle signature for some carbonatites and the influence of post-magmatic processes in others. Immiscibility of liquids of phonolitic composition, derived from mafic alkaline parental magmas, has been responsible for the origin of the carbonatites. Close association of alkaline

  8. 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.

  9. Optical Properties of Alkaline Earth Ions Doped Bismuth Borate Glasses

    SciTech Connect

    Kundu, Virender; Dhiman, R. L.; Maan, A. S.; Goyal, D. R.

    2011-07-15

    The optical properties of glasses with composition xLi{sub 2}O(30-x)Bi{sub 2}O{sub 3}-70B{sub 2}O{sub 3}; x = 0, 5, 10, 15 and 20 mol %, prepared by normal melt quench technique were investigated by means of UV-VIS measurement. It was observed that the optical band gap of the present glass system decreases with increasing Li{sub 2}O content up to 15 mol%, and with further increase in lithium oxide content i.e. x>15 mol% the optical band gap increases. It was also observed that the present glass system behaves as an indirect band gap semiconductor.

  10. Synthesis and Characterization of Alkaline-Earth Indium Sulfides

    DTIC Science & Technology

    1990-06-01

    CaS and In2S3 in an evacuated silica ampule, has the normal spinel structure (a = 10.77 ).1 This report is surprising, since the large Ca 2 + ion would...Ca3.1In6.6S13, 4 has been synthesized as yellow whiskers by iodine transport of a mixture of CaS and In2S3 . An X-ray single-crystal structure determination 5...mixture of CaS (Cerac 99.99%) and In2S3 (prepared from In(NO3)3 and H2S at 750’C) was pre-reacted in a graphite crucible in an evacuated silica

  11. Dissolution of alkaline earth sulfates in the presence of montmorillonite

    USGS Publications Warehouse

    Eberl, D.D.; Landa, E.R.

    1985-01-01

    In a study of the effect of montmorillonite on the dissolution of BaSO4 (barite), SrSO4 (celestite), and 226Ra from U mill tailings, it was found that: (1) More of these substances dissolve in an aqueous system that contains montmorillonite than dissolve in a similar system without clay, due to the ion exchange properties of the clay; (2) Na-montmorillonite is more effective in aiding dissolution than is Ca-montmorillonite; (3) the amount of Ra that moves from mill tailings to an exchanger increases as solution sulfate activity decreases. Leaching experiments suggest that 226Ra from H2SO4-circuit U mill tailings from Edgemont, South Dakota, is not present as pure Ra sulfate or as an impurity in anhydrite or gypsum; it is less soluble, and probably occurs as a trace constituent in barite.

  12. Aluminum/alkaline earth metal composites and method for producing

    DOEpatents

    Russell, Alan M; Anderson, Iver E; Kim, Hyong J; Freichs, Andrew E

    2014-02-11

    A composite is provided having an electrically conducting Al matrix and elongated filaments comprising Ca and/or Sr and/or Ba disposed in the matrix and extending along a longitudinal axis of the composite. The filaments initially comprise Ca and/or Sr and/or Ba metal or allow and then may be reacted with the Al matrix to form a strengthening intermetallic compound comprising Al and Ca and/or Sr and/or Ba. The composite is useful as a long-distance, high voltage power transmission conductor.

  13. Atomistic simulation of defects in alkaline-earth fluorohalide crystals

    NASA Astrophysics Data System (ADS)

    Baetzold, Roger C.

    1987-12-01

    Defect properties of BaFBr, BaFCl, and SrFCl were calculated using the atomistic simulation technique. Two-body potentials were developed starting from potentials in related crystals or calculated by the electron-gas method and then fit to minimize strain in the equilibrium structure. Agreement of calculated elastic, dielectric, and cohesive properties with available experimental and theoretical data was reasonable. Generally, Frenkel energies for the larger-size halogen ion were less than for the fluorine ion and less than the Schottky energy for the metal, fluoride, and other halide ions set. A Schottky energy for vacancies of the metal ion and two of the larger-size halide ions was small. Energies of formation of Vk and H centers were computed with the aid of thermodynamic cycles. The most stable Vk center forms on the halide ion site where the Madelung potential is most favorable for holes. H centers occupy off-center sites in these low-symmetry materials. Stable geometries are discussed.

  14. Soft-mode transitions of alkaline-earth 122 pnictides

    NASA Astrophysics Data System (ADS)

    Widom, Michael; Quader, Khandker

    A -122 pnictides (A=Ca, Sr, Ba) exhibit three pressure-driven transitions: a first order enthalpic transition at PH from the striped AFM orthorhombic (OR) to a tetragonal (T) or a collapsed tetragonal (cT) phase; a transition at PM >PH from the metastable AFM OR to a T or cT phase; a Lifshitz transition at PL that causes T to collapse to a cT phase. Transitions at PH and PL were previously examined through total energy and band structure calculations. Here we address the transition at PM, beyond which the metastable AFM OR state ceases to exist. We show this transition occurs through a loss of elastic stability caused by softening of a shear mode associated with stretching along the c-axis. Simultaneously, magnetism and orthorhombicity approach limiting values with an approximately square-root singularity. Together these suggest a strong magneto-elastic coupling that may be relevant to a further understanding of the A-122-pnictides under pressure. This work was supported in part by the DOE under Grant DE-SC0014506.

  15. Fatigue crack growth in lithium hydride

    SciTech Connect

    Healy, T.E.

    1993-09-01

    Subcritical fatigue crack growth, from cyclic tensile loading, was demonstrated in warm pressed Polycrystalline lithium hydride. Experiments were performed with cyclic tension-tension crack opening (mode I) loads applied to a pre-cracked compact type specimen in an argon environment at a temperature of 21C (70F). The fatigue crack growth was found to occur between 7.56 {times} 10{sup {minus}ll} M/cycle (2.98 {times} l0{sup {minus}9} in/cycle) and 2.35 {times} l0{sup {minus}8} m/cycle (9.24{times}10{sup {minus}7} in/cycle) for a range of stress intensity factors between 1.04 MPa{center_dot}{radical}m (0.95 ksi{center_dot}{radical}in) and 1.49 MPa{center_dot}{radical}m (1.36 ksi{center_dot}{radical}in). The rate of fatigue crack growth from cyclic tensile loading was found to be in excess of crack growth from sustained loading at an equivalent stress intensity factor. Furthermore, a fatigue threshold was not evident from the acquired data.

  16. Permeation rates for RTF metal hydride vessels

    SciTech Connect

    Klein, J.E.

    1992-05-21

    Contamination rates have been estimated for the RTF nitrogen heating and cooling system (NH and CS) due to tritium permeation through the walls of metal hydride vessels. Tritium contamination of the NH and CS will be seen shortly after start-up of the RTF with the majority of it coming from the TCAP units. Contamination rates of the NH and CS are estimated to exceed 400 Ci/year after three years of operation and will elevate tritium concentrations in the NH and CS above 6 {times} 10{sup {minus}3} {mu}Ci/cc. To reduce tritium activity in the NH and CS, a stripper or ``getter`` bed may need to be installed in the NH and CS. Increasing the purge rate of nitrogen from the NH and CS is shown to be an impractical method for reducing tritium activity due to the high purge rates required. Stripping of the NH and CS nitrogen in the glove box stripper system will give a temporary lowering of tritium activity in the NH and CS, but tritium activity will return to its previous level in approximately two weeks.

  17. Transition-Metal Hydride Radical Cations.

    PubMed

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

    2016-08-10

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

  18. Charging efficiency of metal-hydride electrodes

    NASA Astrophysics Data System (ADS)

    Chen, J.; Dou, S. X.; Bradhurst, D.; Liu, H. K.

    The charging efficiencies of MmNi 5, MmNi 4.5Mn 0.5, MmNi 3.8Co 0.7Mn 0.5, ZrV 0.6Ni 1.4, ZrV 0.6Mn 0.4Ni 1.0, ZrV 0.6Mn 0.4Co 0.2Ni 0.8 allay electrodes (Mm = Mischmetal) are investigated in terms of hydrogen evolution. Experiments are conducted to optimize: (i) elemental composition of the MmNi 5 system and Zr-based Laves-phase hydrogen storage alloys; (ii) additive materials, such as cobalt powder, nickel powder, Teflonized carbons, and acetylene black; (iii) the proportion of the additives in the alloy; (iv) the best percentage of the composite additives in the metal-hydride electrodes. The results show that the electrode activation, charging efficiency and high-rate discharge depend greatly on the active materials, as well as the type and the amount of the additives in the electrodes.

  19. Comparison of the interactions in the rare gas hydride and Group 2 metal hydride anions.

    PubMed

    Harris, Joe P; Manship, Daniel R; Breckenridge, W H; Wright, Timothy G

    2014-02-28

    We study both the rare gas hydride anions, RG-H(-) (RG = He-Rn) and Group 2 (Group IIa) metal hydride anions, MIIaH(-) (MIIa = Be-Ra), calculating potential energy curves at the CCSD(T) level with augmented quadruple and quintuple basis sets, and extrapolating the results to the basis set limit. We report spectroscopic parameters obtained from these curves; additionally, we study the Be-He complex. While the RG-H(-) and Be-He species are weakly bound, we show that, as with the previously studied BeH(-) and MgH(-) species, the other MIIaH(-) species are strongly bound, despite the interactions nominally also being between two closed shell species: M(ns(2)) and H(-)(1s(2)). We gain insight into the interactions using contour plots of the electron density changes and population analyses. For both series, the calculated dissociation energy is significantly less than the ion/induced-dipole attraction term, confirming that electron repulsion is important in these species; this effect is more dramatic for the MIIaH(-) species than for RG-H(-). Our analyses lead us to conclude that the stronger interaction in the case of the MIIaH(-) species arises from sp and spd hybridization, which allows electron density on the MIIa atom to move away from the incoming H(-).

  20. Multidimensional simulations of hydrides during fuel rod lifecycle

    NASA Astrophysics Data System (ADS)

    Stafford, D. S.

    2015-11-01

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

  1. 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.

  2. Synthesis and acid digestion of biomorphic ceramics: determination of alkaline and alkaline earth ions.

    PubMed

    Bosch Ojeda, Catalina; Sánchez Rojas, Fuensanta; Cano Pavón, José Manuel

    2007-09-01

    Ceramic and glass are some of the more recent engineering materials and those that are most resistant to environmental conditions. They belong to advanced materials in that they are being developed for the aerospace and electronics industries. In the last decade, a new class of ceramic materials has been the focus of particular attention. The materials were produced with natural, renewable resources (wood or wood-based products). In this work, we have synthesised a new biomorphic ceramic material from oak wood and Si infiltration. After the material characterization, we have optimized the dissolution of the sample by acid attack in an oven under microwave irradiation. Experimental designs were used as a multivariate strategy for the evaluation of the effects of varying several variables at the same time. The optimization was performed in two steps using factorial design for preliminary evaluation and a Draper-Lin design for determination of the critical experimental conditions. Five variables (time, power, volume of HNO3, volume H2SO4 and volume of HF) were considered as factors and as a response the concentration of different metal ions in the optimization process. Interactions between analytical factors and their optimal levels were investigated using a Draper-Lin design.

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

    DOEpatents

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

    1999-03-30

    An at least ternary metal alloy of the formula AB{sub (Z-Y)}X{sub (Y)} is disclosed. In this formula, A is selected from the rare earth elements, B is selected from the elements of Groups 8, 9, and 10 of the Periodic Table of the Elements, and X includes at least one of the following: antimony, arsenic, germanium, tin or bismuth. Z is greater than or equal to 4.8 and less than or equal to 6.0. Y is greater than 0 and less than 1. Ternary or higher-order substitutions to the base AB{sub 5} alloys that form strong kinetic interactions with the predominant metals in the base metal hydride are used to form metal alloys with high structural integrity after multiple cycles of hydrogen sorption. 16 figs.

  4. Investigation of metal hydride materials as hydrogen reservoirs for metal-hydrogen batteries

    NASA Technical Reports Server (NTRS)

    ONISCHAK

    1976-01-01

    The performance and suitability of various metal hydride materials were examined for use as possible hydrogen storage reservoirs for secondary metal-hydrogen batteries. Lanthanum pentanickel hydride appears as a probable candidate in terms of stable hydrogen supply under feasible thermal conditions. A kinetic model describing the decomposition rate data of the hydride has been developed.

  5. The coordination chemistry of organo-hydride donors: new prospects for efficient multi-electron reduction.

    PubMed

    McSkimming, Alex; Colbran, Stephen B

    2013-06-21

    In biological reduction processes the dihydronicotinamides NAD(P)H often transfer hydride to an unsaturated substrate bound within an enzyme active site. In many cases, metal ions in the active site bind, polarize and thereby activate the substrate to direct attack by hydride from NAD(P)H cofactor. This review looks more widely at the metal coordination chemistry of organic donors of hydride ion--organo-hydrides--such as dihydronicotinamides, other dihydropyridines including Hantzsch's ester and dihydroacridine derivatives, those derived from five-membered heterocycles including the benzimidazolines and benzoxazolines, and all-aliphatic hydride donors such as hexadiene and hexadienyl anion derivatives. The hydride donor properties--hydricities--of organo-hydrides and how these are affected by metal ions are discussed. The coordination chemistry of organo-hydrides is critically surveyed and the use of metal-organo-hydride systems in electrochemically-, photochemically- and chemically-driven reductions of unsaturated organic and inorganic (e.g. carbon dioxide) substrates is highlighted. The sustainable electrocatalytic, photochemical or chemical regeneration of organo-hydrides such as NAD(P)H, including for driving enzyme-catalysed reactions, is summarised and opportunities for development are indicated. Finally, new prospects are identified for metal-organo-hydride systems as catalysts for organic transformations involving 'hydride-borrowing' and for sustainable multi-electron reductions of unsaturated organic and inorganic substrates directly driven by electricity or light or by renewable reductants such as formate/formic acid.

  6. Energetics of Amino Acid Synthesis in Alkaline Hydrothermal Environments.

    PubMed

    Kitadai, Norio

    2015-12-01

    Alkaline hydrothermal systems have received considerable attention as candidates for the origin and evolution of life on the primitive Earth. Nevertheless, sufficient information has not yet been obtained for the thermodynamic properties of amino acids, which are necessary components for life, at high temperatures and alkaline pH. These properties were estimated using experimental high-temperature volume and heat capacity data reported in the literature for several amino acids, together with correlation algorithms and the revised Helgeson-Kirkham-Flowers (HKF) equations of state. This approach enabled determination of a complete set of the standard molal thermodynamic data and the revised HKF parameters for the 20 protein amino acids in their zwitterionic and ionization states. The obtained dataset was then used to evaluate the energetics of amino acid syntheses from simple inorganic precursors (CO2, H2, NH3 and H2S) in a simulated alkaline hydrothermal system on the Hadean Earth. Results show that mixing between CO2-rich seawater and the H2-rich hydrothermal fluid can produce energetically favorable conditions for amino acid syntheses, particularly in the lower-temperature region of such systems. Together with data related to the pH and temperature dependences of the energetics of amino acid polymerizations presented in earlier reports, these results suggest the following. Hadean alkaline hydrothermal settings, where steep pH and temperature gradients may have existed between cool, slightly acidic Hadean ocean water and hot, alkaline hydrothermal fluids at the vent-ocean interface, may be energetically the most suitable environment for the synthesis and polymerization of amino acids.

  7. Energetics of Amino Acid Synthesis in Alkaline Hydrothermal Environments

    NASA Astrophysics Data System (ADS)

    Kitadai, Norio

    2015-12-01

    Alkaline hydrothermal systems have received considerable attention as candidates for the origin and evolution of life on the primitive Earth. Nevertheless, sufficient information has not yet been obtained for the thermodynamic properties of amino acids, which are necessary components for life, at high temperatures and alkaline pH. These properties were estimated using experimental high-temperature volume and heat capacity data reported in the literature for several amino acids, together with correlation algorithms and the revised Helgeson-Kirkham-Flowers (HKF) equations of state. This approach enabled determination of a complete set of the standard molal thermodynamic data and the revised HKF parameters for the 20 protein amino acids in their zwitterionic and ionization states. The obtained dataset was then used to evaluate the energetics of amino acid syntheses from simple inorganic precursors (CO2, H2, NH3 and H2S) in a simulated alkaline hydrothermal system on the Hadean Earth. Results show that mixing between CO2-rich seawater and the H2-rich hydrothermal fluid can produce energetically favorable conditions for amino acid syntheses, particularly in the lower-temperature region of such systems. Together with data related to the pH and temperature dependences of the energetics of amino acid polymerizations presented in earlier reports, these results suggest the following. Hadean alkaline hydrothermal settings, where steep pH and temperature gradients may have existed between cool, slightly acidic Hadean ocean water and hot, alkaline hydrothermal fluids at the vent-ocean interface, may be energetically the most suitable environment for the synthesis and polymerization of amino acids.

  8. 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

  9. A nickel metal hydride battery for electric vehicles.

    PubMed

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

    1993-04-09

    Widespread use of electric vehicles can have significant impact on urban air quality, national energy independence, and international balance of trade. 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.

  10. Investigation of metal hydride nanoparticles templated in metal organic frameworks.

    SciTech Connect

    Jacobs, Benjamin W.; Herberg, Julie L.; Highley, Aaron M.; Grossman, Jeffrey; Wagner, Lucas; Bhakta, Raghu; Peaslee, D.; Allendorf, Mark D.; Liu, X.; Behrens, Richard, Jr.; Majzoub, Eric H.

    2010-11-01

    Hydrogen is proposed as an ideal carrier for storage, transport, and conversion of energy. However, its storage is a key problem in the development of hydrogen economy. Metal hydrides hold promise in effectively storing hydrogen. For this reason, metal hydrides have been the focus of intensive research. The chemical bonds in light metal hydrides are predominantly covalent, polar covalent or ionic. These bonds are often strong, resulting in high thermodynamic stability and low equilibrium hydrogen pressures. In addition, the directionality of the covalent/ionic bonds in these systems leads to large activation barriers for atomic motion, resulting in slow hydrogen sorption kinetics and limited reversibility. One method for enhancing reaction kinetics is to reduce the size of the metal hydrides to nano scale. This method exploits the short diffusion distances and constrained environment that exist in nanoscale hydride materials. In order to reduce the particle size of metal hydrides, mechanical ball milling is widely used. However, microscopic mechanisms responsible for the changes in kinetics resulting from ball milling are still being investigated. The objective of this work is to use metal organic frameworks (MOFs) as templates for the synthesis of nano-scale NaAlH4 particles, to measure the H2 desorption kinetics and thermodynamics, and to determine quantitative differences from corresponding bulk properties. Metal-organic frameworks (MOFs) offer an attractive alternative to traditional scaffolds because their ordered crystalline lattice provides a highly controlled and understandable environment. The present work demonstrates that MOFs are stable hosts for metal hydrides and their reactive precursors and that they can be used as templates to form metal hydride nanoclusters on the scale of their pores (1-2 nm). We find that using the MOF HKUST-1 as template, NaAlH4 nanoclusters as small as 8 formula units can be synthesized inside the pores. A detailed picture of

  11. 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.

  12. 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

  13. Metal hydride hydrogen compression: Recent advances and future prospects

    SciTech Connect

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

    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 and 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.

  14. Catalytic Diversity in Alkaline Hydrothermal Vent Systems on Ocean Worlds

    NASA Astrophysics Data System (ADS)

    Cameron, Ryan D.; Barge, Laura; Chin, Keith B.; Doloboff, Ivria J.; Flores, Erika; Hammer, Arden C.; Sobron, Pablo; Russell, Michael J.; Kanik, Isik

    2016-10-01

    Hydrothermal systems formed by serpentinization can create moderate-temperature, alkaline systems and it is possible that this type of vent could exist on icy worlds such as Europa which have water-rock interfaces. It has been proposed that some prebiotic chemistry responsible for the emergence of life on Earth and possibly other wet and icy worlds could occur as a result ofredox potential and pH gradients in submarine alkaline hydrothermal vents (Russell et al., 2014). Hydrothermal chimneys formed in laboratory simulations of alkaline vents under early Earth conditions have precipitate membranes that contain minerals such as iron sulfides, which are hypothesized to catalyze reduction of CO2 (Yamaguchi et al. 2014, Roldan et al. 2014) leading to further organic synthesis. This CO2 reduction process may be affected by other trace components in the chimney, e.g. nickel or organic molecules. We have conducted experiments to investigate catalytic properties of iron and iron-nickel sulfides containing organic dopants in slightly acidic ocean simulants relevant to early Earth or possibly ocean worlds. We find that the electrochemical properties of the chimney as well as the morphology/chemistry of the precipitate are affected by the concentration and type of organics present. These results imply that synthesis of organics in water-rock systems on ocean worlds may lead to hydrothermal precipitates which can incorporate these organic into the mineral matrix and may affect the role of gradients in alkaline vent systems.Therefore, further understanding on the electroactive roles of various organic species within hydrothermal chimneys will have important implications for habitability as well as prebiotic chemistry. This work is funded by NASA Astrobiology Institute JPL Icy Worlds Team and a NAI Director's Discretionary Fund award.Yamaguchi A. et al. (2014) Electrochimica Acta, 141, 311-318.Russell, M. J. et al. (2014), Astrobiology, 14, 308-43.Roldan, A. (2014) Chem. Comm. 51

  15. High-Spin Cobalt Hydrides for Catalysis

    SciTech Connect

    Holland, Patrick L.

    2013-08-29

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

  16. 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.

  17. Hydride formation in core-shell alloyed metal nanoparticles

    NASA Astrophysics Data System (ADS)

    Zhdanov, Vladimir P.

    2016-07-01

    The model and analysis presented are focused on hydride formation in nanoparticles with a Pd shell and a core formed by another metal. The arrangement of metal atoms is assumed to be coherent (no dislocations). The lattice strain distribution, elastic energy, and chemical potential of hydrogen atoms are scrutinized. The slope of the chemical potential (as a function of hydrogen uptake) is demonstrated to decrease with increasing the core volume, and accordingly the critical temperature for hydride formation and the corresponding hysteresis loops are predicted to decrease as well.

  18. 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.

  19. Ab-initio study of transition metal hydrides

    SciTech Connect

    Sharma, Ramesh; Shukla, Seema Dwivedi, Shalini Sharma, Yamini

    2014-04-24

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

  20. Exploring "aerogen-hydride" interactions between ZOF2 (Z = Kr, Xe) and metal hydrides: An ab initio study

    NASA Astrophysics Data System (ADS)

    Esrafili, Mehdi D.; Mohammadian-Sabet, Fariba

    2016-06-01

    In this work, a new σ-hole interaction formed between ZOF2 (Z = Kr and Xe) as the Lewis acid and a series of metal-hydrides HMX (M = Be, Mg, Zn and X = H, F, CN, CH3) is reported. The nature of this interaction, called "aerogen-hydride" interaction, is unveiled by molecular electrostatic potential, non-covalent interaction, quantum theory of atoms in molecules and natural bond orbital analyses. Our results indicate that the aerogen-hydride interactions are quite strong and can be comparable in strength to other σ-hole bonds. An important charge-transfer interaction is also associated with the formation of OF2Z⋯HMX complexes.

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

    SciTech Connect

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

    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.

  2. When can ocean acidification impacts be detected from decadal alkalinity measurements?

    NASA Astrophysics Data System (ADS)

    Carter, B. R.; Frölicher, T. L.; Dunne, J. P.; Rodgers, K. B.; Slater, R. D.; Sarmiento, J. L.

    2016-04-01

    We use a large initial condition suite of simulations (30 runs) with an Earth system model to assess the detectability of biogeochemical impacts of ocean acidification (OA) on the marine alkalinity distribution from decadally repeated hydrographic measurements such as those produced by the Global Ship-Based Hydrographic Investigations Program (GO-SHIP). Detection of these impacts is complicated by alkalinity changes from variability and long-term trends in freshwater and organic matter cycling and ocean circulation. In our ensemble simulation, variability in freshwater cycling generates large changes in alkalinity that obscure the changes of interest and prevent the attribution of observed alkalinity redistribution to OA. These complications from freshwater cycling can be mostly avoided through salinity normalization of alkalinity. With the salinity-normalized alkalinity, modeled OA impacts are broadly detectable in the surface of the subtropical gyres by 2030. Discrepancies between this finding and the finding of an earlier analysis suggest that these estimates are strongly sensitive to the patterns of calcium carbonate export simulated by the model. OA impacts are detectable later in the subpolar and equatorial regions due to slower responses of alkalinity to OA in these regions and greater seasonal equatorial alkalinity variability. OA impacts are detectable later at depth despite lower variability due to smaller rates of change and consistent measurement uncertainty.

  3. Alkali-metal/alkaline-earth-metal fluorine beryllium borate NaSr{sub 3}Be{sub 3}B{sub 3}O{sub 9}F{sub 4} with large nonlinear optical properties in the deep-ultraviolet region

    SciTech Connect

    Reshak, A. H.; Huang, Hongwei; Kamarudin, H.; Auluck, S.

    2015-02-28

    The linear optical response and second harmonic generation (SHG) in alkali-metal/alkaline-earth-metal fluorine beryllium borate NaSr{sub 3}Be{sub 3}B{sub 3}O{sub 9}F{sub 4} are investigated by means of density functional theory. Calculations are performed using four types of exchange correlations: Ceperley-Alder local density approximation, Perdew Burke and Ernzerhof general gradient approximation, Engel-Vosko generalized gradient approximation, and the recently modified Becke-Johnson potential (mBJ). The mBJ approach brings the calculated band gap (7.20 eV) in excellent agreement with the experimental one (7.28 eV). The calculated values of the uniaxial anisotropy δε=−0.076 and the birefringence Δn(0)=0.052 indicate considerable anisotropy in the linear optical properties, which makes it favorable for the second harmonic generation. The dominant component of the second harmonic generation is χ{sub 111}{sup (2)}(ω). The value of |χ{sub 111}{sup (2)}(ω)| is about 1.2 pm/V at λ = 1064 nm in agreement with previous calculations. To analyze the origin of the high SHG of NaSr{sub 3}Be{sub 3}B{sub 3}O{sub 9}F{sub 4} single crystals, we have correlated the features of |χ{sub 111}{sup (2)}(ω)| spectra with the features of ε{sub 2}(ω) spectra as a function of ω/2 and ω. From the calculated dominant component |χ{sub 111}{sup (2)}(ω)|, we find that the microscopic first hyperpolarizability, β{sub 111}, the vector components along the dipole moment direction is 0.5 × 10{sup −30} esu at static limit and 0.6 × 10{sup −30} esu at λ = 1064 nm.

  4. Zinc electrode in alkaline electrolyte

    SciTech Connect

    McBreen, J.

    1995-12-31

    The zinc electrode in alkaline electrolyte is unusual in that supersaturated zincate solutions can form during discharge and spongy or mossy zinc deposits can form on charge at low overvoltages. The effect of additives on regular pasted ZnO electrodes and calcium zincate electrodes is discussed. The paper also reports on in situ x-ray absorption (XAS) results on mossy zinc deposits.

  5. Heat-mass flow enhancement system for a metal hydride assembly

    NASA Astrophysics Data System (ADS)

    Argabright, T. A.

    1985-02-01

    Southern California Gas Company and Solar Turbines Incorporated are cooperating in the development and demonstration of a metal hydride/chemical heat pump (MHHP). In the design of the MHHP, heat transfer was considered to be the key technical study area. The goal of this effort is improved heat transfer and reduced thermal mass in a hydride heat exchanger/containment assembly. Phase 1 resulted in the detailed design of an advanced hydride heat exchanger. Phase 2 consisted of the experimental verification of the hydride alloy design data, fabrication of the hydride heat exchanger module components, heat transfer testing of the single heat exchanger element and preliminary performance testing of the entire module. Phase 3 was devoted to the complete characterization of the hydride heat exchanger modules through further operation and testing. A review of other possible hydride heat transfer concepts was also conducted in Phase 2.

  6. Earth Resources

    ERIC Educational Resources Information Center

    Brewer, Tom

    1970-01-01

    Reviews some of the more concerted, large-scale efforts in the earth resources areas" in order to help the computer community obtain insights into the activities it can jointly particpate in withthe earth resources community." (Author)

  7. Hydride vapor phase epitaxy of aluminum nitride

    NASA Astrophysics Data System (ADS)

    Kamber, Derrick Shane

    AlN is a promising substrate material for AlGaN-based UV optoelectronic devices and high-power, high-frequency electronic devices. Since large-area bulk AlN crystals are not readily available, one approach to prepare AlN substrates is to heteroepitaxially deposit thick (e.g., 10-300+ mum) AlN layers by hydride vapor phase epitaxy. Initial efforts focused on growing AlN layers on sapphire substrates with growth rates up to 75 mum/hr. The resulting layers were colorless, smooth, and specular. Subsurface cracking, attributed to the plastic relief of tensile strain from island coalescence, was observed but did not adversely affect the surface morphology of the AlN layers. The surfaces possessed rms roughnesses as low as 0.316 nm over 5 x 5 mum2 sampling areas, but hexagonal hillock formation was observed for thick films grown at high growth rates. TEM revealed that the threading dislocation (TD) density of the films was 2 x 109 cm-2. The high TD densities for direct growth of AlN films on foreign substrates motivated the development of lateral epitaxial overgrowth approaches for defect reduction. Growth of AlN layers on patterned SiC substrates produced coalesced AlN films possessing TD densities below 8.3 x 106 cm -2 in the laterally grown wing regions, as compared to 1.8 x 109 cm-2 in the seed regions. These films, however, cracked on cooldown due to the difference in thermal expansion coefficients for AlN and SiC. To avoid this cracking, AlN layers were grown on patterned sapphire substrates. Although the films were able to be coalesced and contained few or no cracks, the TDs in these films were not confined to the seed regions. This produced a relatively uniform distribution of TDs over the surfaces of the films, with only a modest reduction in the TD density of 1 x 10 8 cm-2. Selective area growth of AlN was also pursued using Si3N4, SiO2, and Ti masks. Growth selectivity and film coalescence was observed for films grown on each masking material, but none of the

  8. KNH2-KH: a metal amide-hydride solid solution.

    PubMed

    Santoru, Antonio; Pistidda, Claudio; Sørby, Magnus H; Chierotti, Michele R; Garroni, Sebastiano; Pinatel, Eugenio; Karimi, Fahim; Cao, Hujun; Bergemann, Nils; Le, Thi T; Puszkiel, Julián; Gobetto, Roberto; Baricco, Marcello; Hauback, Bjørn C; Klassen, Thomas; Dornheim, Martin

    2016-09-27

    We report for the first time the formation of a metal amide-hydride solid solution. The dissolution of KH into KNH2 leads to an anionic substitution, which decreases the interaction among NH2(-) ions. The rotational properties of the high temperature polymorphs of KNH2 are thereby retained down to room temperature.

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

    DOEpatents

    Congdon, James W.

    2009-03-17

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

  10. Cascades for hydrogen isotope separation using metal hydrides

    SciTech Connect

    Hill, F.B.; Grzetic, V.

    1982-01-01

    Designs are presented for continuous countercurrent hydrogen isotope separation cascades based on the use of metal hydrides. The cascades are made up of pressure swing adsorption (PSA) or temperature swing adsorption (TSA) stages. The designs were evolved from consideration of previously conducted studies of the separation performance of four types of PSA and TSA processes.

  11. 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.

  12. Hydride encapsulation by molecular alkali-metal clusters.

    PubMed

    Haywood, Joanna; Wheatley, Andrew E H

    2008-07-14

    The sequential treatment of group 12 and 13 Lewis acids with alkali-metal organometallics is well established to yield so-called ''ate' complexes, whereby the Lewis-acid metal undergoes nucleophilic attack to give an anion, at least one group 1 metal acting to counter this charge. However, an alternative, less well recognised, reaction pathway involves the Lewis acid abstracting hydride from the organolithium reagent via a beta-elimination mechanism. It has recently been shown that in the presence of N,N'-bidentate ligands this chemistry can be harnessed to yield a new type of molecular main-group metal cluster in which the abstracted LiH is effectively trapped, with the hydride ion occupying an interstitial site in the cluster core. Discussion focuses on the development of this field, detailing advances in our understanding of the roles of Lewis acid, organolithium, and amine substrates in the syntheses of these compounds. Structure-types are discussed, as are efforts to manipulate cluster geometry and composition as well as hydride-coordination. Embryonic mechanistic studies are reported, as well as attempts to generate hydride-encapsulation clusters under catalytic control.

  13. Optimizing Misch-Metal Compositions In Metal Hydride Anodes

    NASA Technical Reports Server (NTRS)

    Bugga, Ratnakumar V.; Halpert, Gerald

    1995-01-01

    Electrochemical cells based on metal hydride anodes investigated experimentally in effort to find anode compositions maximizing charge/discharge-cycle performances. Experimental anodes contained misch metal alloyed with various proportions of Ni, Co, Mn, and Al, and experiments directed toward optimization of composition of misch metal.

  14. Well-defined transition metal hydrides in catalytic isomerizations.

    PubMed

    Larionov, Evgeny; Li, Houhua; Mazet, Clément

    2014-09-07

    This Feature Article intends to provide an overview of a variety of catalytic isomerization reactions that have been performed using well-defined transition metal hydride precatalysts. A particular emphasis is placed on the underlying mechanistic features of the transformations discussed. These have been categorized depending upon the nature of the substrate and in most cases discussed following a chronological order.

  15. Hydride generation from the Exide load-leveling cells

    NASA Astrophysics Data System (ADS)

    Marr, J. J.; Smaga, J. A.

    1987-05-01

    Stibine and arsine evolution from lead-acid cells in a 36-kWh Exide load-leveling module was measured as this module approached 1900 cycles of operation. A gas-collection apparatus enabled us to determine the maximum and average rates for evolution of both toxic hydrides. Hydride generation began once the cell voltage exceeded 2.4 V. The maximum rate for arsine occurred just above 2.5 V and consistently preceded the peak rate for stibine for each sampled cell. The average rates of hydride generation were found to be 175 g/min for stibine and 12.6 g/min for arsine. The former rate proved to be the critical value in determining safe ventilation requirements for cell off-gases. The minimum airflow requirement was calculated to be 340 L/min per cell. Projections for a hypothetical 1-MWh Exide battery without an abatement system indicated that the normal ventilation capacity in the Battery Energy Storage Test facility provides nearly five times the airflow needed for safe hydride removal.

  16. Nucleotide sequences encoding a thermostable alkaline protease

    DOEpatents

    Wilson, David B.; Lao, Guifang

    1998-01-01

    Nucleotide sequences, derived from a thermophilic actinomycete microorganism, which encode a thermostable alkaline protease are disclosed. Also disclosed are variants of the nucleotide sequences which encode a polypeptide having thermostable alkaline proteolytic activity. Recombinant thermostable alkaline protease or recombinant polypeptide may be obtained by culturing in a medium a host cell genetically engineered to contain and express a nucleotide sequence according to the present invention, and recovering the recombinant thermostable alkaline protease or recombinant polypeptide from the culture medium.

  17. Nucleotide sequences encoding a thermostable alkaline protease

    DOEpatents

    Wilson, D.B.; Lao, G.

    1998-01-06

    Nucleotide sequences, derived from a thermophilic actinomycete microorganism, which encode a thermostable alkaline protease are disclosed. Also disclosed are variants of the nucleotide sequences which encode a polypeptide having thermostable alkaline proteolytic activity. Recombinant thermostable alkaline protease or recombinant polypeptide may be obtained by culturing in a medium a host cell genetically engineered to contain and express a nucleotide sequence according to the present invention, and recovering the recombinant thermostable alkaline protease or recombinant polypeptide from the culture medium. 3 figs.

  18. Hydride Compressor Sorption Cooler and Surface Contamination Issues

    NASA Astrophysics Data System (ADS)

    Bowman, R. C.; Reiter, J. W.; Prina, M.; Kulleck, J. G.; Lanford, W. A.

    2003-07-01

    A continuous-duty hydrogen sorption cryocooler is being developed for the Planck spacecraft, a mission to map the cosmic microwave background beginning in 2007. This cryocooler uses six individual compressor elements (CEs) filled with the hydriding alloy LaNi4.78Sn0.22 to provide high-pressure (50 bar) hydrogen to a Joule-Thomson (J-T) expander and to absorb low-pressure (˜0.3 bar) gas from liquid hydrogen reservoirs cooled to ˜18K. Quadrupole Mass Spectrometry (QMS) showed methane in these hydride beds after cycling during initial operation of laboratory tests of the Planck engineering breadboard (EBB) cooler. These contaminants have caused problems involving plugged J-T expanders. The contaminants probably come from reactions with residual hydrocarbon species on surfaces inside the hydride bed. The hydride bed in each CE is contained in an annular volume called a "gas-gap heat switch," which serves as a reversible, intermittent thermal path to the spacecraft radiator. The gas-gap is either "off" (i.e., its pressure <1.3 Pa), or "on" (i.e., hydrogen gas at ˜4 kPa). The hydrogen pressure is varied with an independent hydride actuator containing ZrNiHx. Early EBB cooler tests showed increasing parasitic heat losses from the inner beds, suggesting residual pressures in the gas gap during its "off" state. The pressure was shown to be due to hydrogen from outgassing from metallic surfaces in the gas gap and hydrogen permeation through the inner sorbent bed wall. This gas accumulation has serious end-of-life implications, as the ZrNi actuator has limited storage capacity and any excess hydrogen would necessarily affect its operation. This paper summarizes experiments on the behavior of hydrogen in the gas gap switch and formation of methane in the CE sorbent beds.

  19. Metal Hydrides as hot carrier cell absorber materials

    NASA Astrophysics Data System (ADS)

    Wang, Pei; Wen, Xiaoming; Shrestha, Santosh; Conibeer, Gavin; Aguey-Zinsou, Kondo-Francois

    2016-09-01

    The hot Carrier Solar Cell (HCSC) allows the photon-induced hot carriers (the carriers with energy larger than the band gap) to be collected before they completely thermalise. The absorber of the HCSC should have a large phononic band gap to supress Klemens Decay, which results in a slow carrier cooling speed. In fact, a large phononic band gap likely exists in a binary compound whose constituent elements have a large mass ratio between each other. Binary hydrides with their overwhelming mass ratio of the constituent elements are important absorber candidates. Study on different types of binary hydrides as potential absorber candidates is presented in this paper. Many binary transition metal hydrides have reported theoretical or experimental phonon dispersion charts which show large phononic band gaps. Among these hydrides, the titanium hydride (TiHX) is outstanding because of its low cost, easy fabrication process and is relatively inert to air and water. A TiHX thin film is fabricated by directly hydrogenating an evaporated titanium thin film. Characterisation shows good crystal quality and the hydrogenation process is believed to be successful. Ultrafast transient absorption (TA) spectroscopy is used to study the electron cooling time of TiHX. The result is very noisy due to the low absorption and transmission of the sample. The evolution of the TA curves has been explained by band to band transition using the calculated band structure of TiH2. Though not reliable due to the high noise, decay time fitting at 700nm and 600nm shows a considerably slow carrier cooling speed of the sample.

  20. Inert blanketing of a hydride bed using typical grade protium

    SciTech Connect

    Klein, J.E.

    2015-03-15

    This paper describes the impact of 500 ppm (0.05%) impurities in protium on the absorption rate of a 9.66 kg LaNi{sub 4.25}Al{sub 0.75} (LANA0.75) metal hydride bed. The presence of 500 ppm or less inerts (i.e. non-hydrogen isotopes) can significantly impact hydrogen bed absorption rates. The impact on reducing absorption rates is significantly greater than predicted assuming uniform temperature, pressure, and compositions throughout the bed. Possible explanations are discussed. One possibility considered was the feed gas contained impurity levels higher than 500 ppm. It was shown that a level of 5000 ppm of inerts would have been necessary to fit the experimental result so this possibility wa dismissed. Another possibility is that the impurities in the protium supply reacted with the hydride material and partially poisoned the hydride. If the hydride were poisoned with CO or another impurity, the removal of the over-pressure gas in the bed would not be expected to allow the hydride loading of the bed to continue as the experimental results showed, so this possibility was also dismissed. The last possibility questions the validity of the calculations. It is assumed in all the calculations that the gas phase composition, temperature, and pressure are uniform throughout the bed. These assumptions are less valid for large beds where there can be large temperature, pressure, and composition gradients throughout the bed. Eventually the impact of 0.05% inerts in protium on bed absorption rate is shown and explained in terms of an increase in inert partial pressure as the bed was loaded.