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Sample records for alkali metal silicate

  1. Alkali-metal silicate binders and methods of manufacture

    NASA Technical Reports Server (NTRS)

    Schutt, J. B. (Inventor)

    1979-01-01

    A paint binder is described which uses a potassium or sodium silicate dispersion having a silicon dioxide to alkali-metal oxide mol ratio of from 4.8:1 to 6.0:1. The binder exhibits stability during both manufacture and storage. The process of making the binder is predictable and repeatable and the binder may be made with inexpensive components. The high mol ratio is achieved with the inclusion of a silicon dioxide hydrogel. The binder, which also employs a silicone, is in the final form of a hydrogel sol.

  2. Alkali Silicate Vehicle Forms Durable, Fireproof Paint

    NASA Technical Reports Server (NTRS)

    Schutt, John B.; Seindenberg, Benjamin

    1964-01-01

    The problem: To develop a paint for use on satellites or space vehicles that exhibits high resistance to cracking, peeling, or flaking when subjected to a wide range of temperatures. Organic coatings will partially meet the required specifications but have the inherent disadvantage of combustibility. Alkali-silicate binders, used in some industrial coatings and adhesives, show evidence of forming a fireproof paint, but the problem of high surface-tension, a characteristic of alkali silicates, has not been resolved. The solution: Use of a suitable non-ionic wetting agent combined with a paint incorporating alkali silicate as the binder.

  3. Alkali metal nitrate purification

    DOEpatents

    Fiorucci, Louis C.; Morgan, Michael J.

    1986-02-04

    A process is disclosed for removing contaminants from impure alkali metal nitrates containing them. The process comprises heating the impure alkali metal nitrates in solution form or molten form at a temperature and for a time sufficient to effect precipitation of solid impurities and separating the solid impurities from the resulting purified alkali metal nitrates. The resulting purified alkali metal nitrates in solution form may be heated to evaporate water therefrom to produce purified molten alkali metal nitrates suitable for use as a heat transfer medium. If desired, the purified molten form may be granulated and cooled to form discrete solid particles of purified alkali metal nitrates.

  4. High-temperature, high-pressure hydrothermal synthesis, characterization, and structural relationships of mixed-alkali metals uranyl silicates

    NASA Astrophysics Data System (ADS)

    Chen, Yi-Hsin; Liu, Hsin-Kuan; Chang, Wen-Jung; Tzou, Der-Lii; Lii, Kwang-Hwa

    2016-04-01

    Three mixed-alkali metals uranyl silicates, Na3K3[(UO2)3(Si2O7)2]·2H2O (1), Na3Rb3[(UO2)3(Si2O7)2] (2), and Na6Rb4[(UO2)4Si12O33] (3), have been synthesized by high-temperature, high-pressure hydrothermal reactions at 550 °C and 1440 bar, and characterized by single-crystal X-ray diffraction, photoluminescence, and thermogravimetric analysis. Compound 1 and 2 are isostructural and contain layers of uranyl disilicate. The smaller cation, Na+, is located in the intralayer channels, whereas the larger cations, K+ and Rb+, and water molecule are located in the interlayer region. The absence of lattice water in 2 can be understood according to the valence-matching principle. The structure is related to that of a previously reported mixed-valence uranium(V,VI) silicate. Compound 3 adopts a 3D framework structure and contains a unique unbranched dreier fourfold silicate chain with the structural formula {uB,41∞}[3Si12O33] formed of Q2, Q3, and Q4 Si. The connectivity of the Si atoms in the Si12O3318- anion can be interpreted on the basis of Zintl-Klemm concept. Crystal data for compound 1: triclinic, P-1, a=5.7981(2) Å, b=7.5875(3) Å, c=12.8068(5) Å, α=103.593(2)°, β=102.879(2)°, γ=90.064(2)°, V=533.00(3) Å3, Z=1, R1=0.0278; compound 2: triclinic, P-1, a=5.7993(3) Å, b=7.5745(3) Å, c=12.9369(6) Å, α=78.265(2)°, β=79.137(2)°, γ=89.936(2)°, V=546.02(4) Å3, Z=1, R1=0.0287; compound 3: monoclinic, C2/m, a=23.748(1) Å, b=7.3301(3) Å, c=15.2556(7) Å, β=129.116(2)°, V=2060.4(2) Å3, Z=2, R1=0.0304.

  5. Alkali metal ionization detector

    DOEpatents

    Bauerle, James E.; Reed, William H.; Berkey, Edgar

    1978-01-01

    Variations in the conventional filament and collector electrodes of an alkali metal ionization detector, including the substitution of helical electrode configurations for either the conventional wire filament or flat plate collector; or, the substitution of a plurality of discrete filament electrodes providing an in situ capability for transferring from an operationally defective filament electrode to a previously unused filament electrode without removing the alkali metal ionization detector from the monitored environment. In particular, the helical collector arrangement which is coaxially disposed about the filament electrode, i.e. the thermal ionizer, provides an improved collection of positive ions developed by the filament electrode. The helical filament design, on the other hand, provides the advantage of an increased surface area for ionization of alkali metal-bearing species in a monitored gas environment as well as providing a relatively strong electric field for collecting the ions at the collector electrode about which the helical filament electrode is coaxially positioned. Alternatively, both the filament and collector electrodes can be helical. Furthermore, the operation of the conventional alkali metal ionization detector as a leak detector can be simplified as to cost and complexity, by operating the detector at a reduced collector potential while maintaining the sensitivity of the alkali metal ionization detector adequate for the relatively low concentration of alkali vapor and aerosol typically encountered in leak detection applications.

  6. Methods of recovering alkali metals

    DOEpatents

    Krumhansl, James L; Rigali, Mark J

    2014-03-04

    Approaches for alkali metal extraction, sequestration and recovery are described. For example, a method of recovering alkali metals includes providing a CST or CST-like (e.g., small pore zeolite) material. The alkali metal species is scavenged from the liquid mixture by the CST or CST-like material. The alkali metal species is extracted from the CST or CST-like material.

  7. Alkali metal ion battery with bimetallic electrode

    SciTech Connect

    Boysen, Dane A; Bradwell, David J; Jiang, Kai; Kim, Hojong; Ortiz, Luis A; Sadoway, Donald R; Tomaszowska, Alina A; Wei, Weifeng; Wang, Kangli

    2015-04-07

    Electrochemical cells having molten electrodes having an alkali metal provide receipt and delivery of power by transporting atoms of the alkali metal between electrode environments of disparate chemical potentials through an electrochemical pathway comprising a salt of the alkali metal. The chemical potential of the alkali metal is decreased when combined with one or more non-alkali metals, thus producing a voltage between an electrode comprising the molten the alkali metal and the electrode comprising the combined alkali/non-alkali metals.

  8. Hydrothermal alkali metal recovery process

    DOEpatents

    Wolfs, Denise Y.; Clavenna, Le Roy R.; Eakman, James M.; Kalina, Theodore

    1980-01-01

    In a coal gasification operation or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein solid particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles by treating them with a calcium or magnesium-containing compound in the presence of water at a temperature between about 250.degree. F. and about 700.degree. F. and in the presence of an added base to establish a pH during the treatment step that is higher than would otherwise be possible without the addition of the base. During the treating process the relatively high pH facilitates the conversion of water-insoluble alkali metal compounds in the alkali metal residues into water-soluble alkali metal constituents. The resultant aqueous solution containing water-soluble alkali metal constituents is then separated from the residue solids, which consist of the treated particles and any insoluble materials formed during the treatment step, and recycled to the gasification process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst. Preferably, the base that is added during the treatment step is an alkali metal hydroxide obtained by water washing the residue solids produced during the treatment step.

  9. Carbonation of metal silicates for long-term CO.sub.2 sequestration

    DOEpatents

    Blencoe, James G.; Palmer, Donald A.; Anovitz, Lawrence M.; Beard, James S.

    2012-02-14

    In a preferred embodiment, the invention relates to a process of sequestering carbon dioxide. The process comprises the steps of: (a) reacting a metal silicate with a caustic alkali-metal hydroxide to produce a hydroxide of the metal formerly contained in the silicate; (b) reacting carbon dioxide with at least one of a caustic alkali-metal hydroxide and an alkali-metal silicate to produce at least one of an alkali-metal carbonate and an alkali-metal bicarbonate; and (c) reacting the metal hydroxide product of step (a) with at least one of the alkali-metal carbonate and the alkali-metal bicarbonate produced in step (b) to produce a carbonate of the metal formerly contained in the metal silicate of step (a).

  10. Carbonation of metal silicates for long-term CO2 sequestration

    DOEpatents

    Blencoe, James G; Palmer, Donald A; Anovitz, Lawrence M; Beard, James S

    2014-03-18

    In a preferred embodiment, the invention relates to a process of sequestering carbon dioxide. The process comprises the steps of: (a) reacting a metal silicate with a caustic alkali-metal hydroxide to produce a hydroxide of the metal formerly contained in the silicate; (b) reacting carbon dioxide with at least one of a caustic alkali-metal hydroxide and an alkali-metal silicate to produce at least one of an alkali-metal carbonate and an alkali-metal bicarbonate; and (c) reacting the metal hydroxide product of step (a) with at least one of the alkali-metal carbonate and the alkali-metal bicarbonate produced in step (b) to produce a carbonate of the metal formerly contained in the metal silicate of step (a).

  11. Electric field-induced softening of alkali silicate glasses

    NASA Astrophysics Data System (ADS)

    McLaren, C.; Heffner, W.; Tessarollo, R.; Raj, R.; Jain, H.

    2015-11-01

    Motivated by the advantages of two-electrode flash sintering over normal sintering, we have investigated the effect of an external electric field on the viscosity of glass. The results show remarkable electric field-induced softening (EFIS), as application of DC field significantly lowers the softening temperature of glass. To establish the origin of EFIS, the effect is compared for single vs. mixed-alkali silicate glasses with fixed mole percentage of the alkali ions such that the mobility of alkali ions is greatly reduced while the basic network structure does not change much. The sodium silicate and lithium-sodium mixed alkali silicate glasses were tested mechanically in situ under compression in external electric field ranging from 0 to 250 V/cm in specially designed equipment. A comparison of data for different compositions indicates a complex mechanical response, which is observed as field-induced viscous flow due to a combination of Joule heating, electrolysis and dielectric breakdown.

  12. Electric field-induced softening of alkali silicate glasses

    SciTech Connect

    McLaren, C.; Heffner, W.; Jain, H.; Tessarollo, R.; Raj, R.

    2015-11-02

    Motivated by the advantages of two-electrode flash sintering over normal sintering, we have investigated the effect of an external electric field on the viscosity of glass. The results show remarkable electric field-induced softening (EFIS), as application of DC field significantly lowers the softening temperature of glass. To establish the origin of EFIS, the effect is compared for single vs. mixed-alkali silicate glasses with fixed mole percentage of the alkali ions such that the mobility of alkali ions is greatly reduced while the basic network structure does not change much. The sodium silicate and lithium-sodium mixed alkali silicate glasses were tested mechanically in situ under compression in external electric field ranging from 0 to 250 V/cm in specially designed equipment. A comparison of data for different compositions indicates a complex mechanical response, which is observed as field-induced viscous flow due to a combination of Joule heating, electrolysis and dielectric breakdown.

  13. Purification of alkali metal nitrates

    DOEpatents

    Fiorucci, Louis C.; Gregory, Kevin M.

    1985-05-14

    A process is disclosed for removing heavy metal contaminants from impure alkali metal nitrates containing them. The process comprises mixing the impure nitrates with sufficient water to form a concentrated aqueous solution of the impure nitrates, adjusting the pH of the resulting solution to within the range of between about 2 and about 7, adding sufficient reducing agent to react with heavy metal contaminants within said solution, adjusting the pH of the solution containing reducing agent to effect precipitation of heavy metal impurities and separating the solid impurities from the resulting purified aqueous solution of alkali metal nitrates. The resulting purified solution of alkali metal nitrates may be heated to evaporate water therefrom to produce purified molten alkali metal nitrate suitable for use as a heat transfer medium. If desired, the purified molten form may be granulated and cooled to form discrete solid particles of alkali metal nitrates.

  14. PROCESS OF RECOVERING ALKALI METALS

    DOEpatents

    Wolkoff, J.

    1961-08-15

    A process is described of recovering alkali metal vapor by sorption on activated alumina, activated carbon, dehydrated zeolite, activated magnesia, or Fuller's earth preheated above the vaporization temperature of the alkali metal and subsequent desorption by heating the solvent under vacuum. (AEC)

  15. Preparation of alkali metal dispersions

    NASA Technical Reports Server (NTRS)

    Rembaum, A.; Landel, R. F. (Inventor)

    1968-01-01

    A method is described for producing alkali metal dispersions of high purity. The dispersions are prepared by varying the equilibrium solubility of the alkali metal in a suitable organic solvent in the presence of aromatic hydrocarbons. The equilibrium variation is produced by temperature change. The size of the particles is controlled by controlling the rate of temperature change.

  16. Upgrading platform using alkali metals

    SciTech Connect

    Gordon, John Howard

    2014-09-09

    A process for removing sulfur, nitrogen or metals from an oil feedstock (such as heavy oil, bitumen, shale oil, etc.) The method involves reacting the oil feedstock with an alkali metal and a radical capping substance. The alkali metal reacts with the metal, sulfur or nitrogen content to form one or more inorganic products and the radical capping substance reacts with the carbon and hydrogen content to form a hydrocarbon phase. The inorganic products may then be separated out from the hydrocarbon phase.

  17. Apparatus enables accurate determination of alkali oxides in alkali metals

    NASA Technical Reports Server (NTRS)

    Dupraw, W. A.; Gahn, R. F.; Graab, J. W.; Maple, W. E.; Rosenblum, L.

    1966-01-01

    Evacuated apparatus determines the alkali oxide content of an alkali metal by separating the metal from the oxide by amalgamation with mercury. The apparatus prevents oxygen and moisture from inadvertently entering the system during the sampling and analytical procedure.

  18. Alkali metal and alkali earth metal gadolinium halide scintillators

    DOEpatents

    Bourret-Courchesne, Edith; Derenzo, Stephen E.; Parms, Shameka; Porter-Chapman, Yetta D.; Wiggins, Latoria K.

    2016-08-02

    The present invention provides for a composition comprising an inorganic scintillator comprising a gadolinium halide, optionally cerium-doped, having the formula A.sub.nGdX.sub.m:Ce; wherein A is nothing, an alkali metal, such as Li or Na, or an alkali earth metal, such as Ba; X is F, Br, Cl, or I; n is an integer from 1 to 2; m is an integer from 4 to 7; and the molar percent of cerium is 0% to 100%. The gadolinium halides or alkali earth metal gadolinium halides are scintillators and produce a bright luminescence upon irradiation by a suitable radiation.

  19. Hydrothermal alkali metal catalyst recovery process

    DOEpatents

    Eakman, James M.; Clavenna, LeRoy R.

    1979-01-01

    In a coal gasification operation or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein solid particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles primarily in the form of water soluble alkali metal formates by treating the particles with a calcium or magnesium-containing compound in the presence of water at a temperature between about 250.degree. F. and about 700.degree. F. and in the presence of added carbon monoxide. During the treating process the water insoluble alkali metal compounds comprising the insoluble alkali metal residues are converted into water soluble alkali metal formates. The resultant aqueous solution containing water soluble alkali metal formates is then separated from the treated particles and any insoluble materials formed during the treatment process, and recycled to the gasification process where the alkali metal formates serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst. This process permits increased recovery of alkali metal constituents, thereby decreasing the overall cost of the gasification process by reducing the amount of makeup alkali metal compounds necessary.

  20. Contributions to the mixed-alkali effect in molecular dynamics simulations of alkali silicate glasses

    NASA Astrophysics Data System (ADS)

    Lammert, Heiko; Heuer, Andreas

    2005-12-01

    The mixed-alkali effect in the cation dynamics in silicate glasses is analyzed via molecular dynamics simulations. Observations suggest a description of the dynamics in terms of stable sites mostly specific to one ionic species. As main contributions to the mixed-alkali slow down longer residence times and an increased probability of correlated backjumps are identified. The slow down is related to the limited accessibility of foreign sites. The mismatch experienced in a foreign site is stronger and more retarding for the larger ions, the smaller ions can be temporarily accommodated. Also correlations between unlike as well as like cations are demonstrated that support cooperative behavior.

  1. Alkali metal/sulfur battery

    DOEpatents

    Anand, Joginder N.

    1978-01-01

    Alkali metal/sulfur batteries in which the electrolyte-separator is a relatively fragile membrane are improved by providing means for separating the molten sulfur/sulfide catholyte from contact with the membrane prior to cooling the cell to temperatures at which the catholyte will solidify. If the catholyte is permitted to solidify while in contact with the membrane, the latter may be damaged. The improvement permits such batteries to be prefilled with catholyte and shipped, at ordinary temperatures.

  2. Superconductivity in alkali metal fullerides

    NASA Astrophysics Data System (ADS)

    Murphy, D. W.; Rosseinsky, M. J.; Haddon, R. C.; Ramirez, A. P.; Hebard, A. F.; Tycko, R.; Fleming, R. M.; Dabbagh, G.

    1991-12-01

    The recent synthesis of macroscopic quantities of spherical molecular carbon compounds, commonly called fullerenes, has stimulated a wide variety of studies of the chemical and physical properties of this novel class of compounds. We discovered that the smallest of the known fullerenes, C 60, could be made conducting and superconducting by reaction with alkali metals. In this paper, an overview of the motivation for these discoveries and some recent results are presented.

  3. Alkali metal sources for OLED devices

    NASA Astrophysics Data System (ADS)

    Cattaneo, Lorena; Longoni, Giorgio; Bonucci, Antonio; Tominetti, Stefano

    2005-07-01

    In OLED organic layers electron injection is improved by using alkali metals as cathodes, to lower work function or, as dopants of organic layer at cathode interface. The creation of an alkali metal layer can be accomplished through conventional physical vapor deposition from a heated dispenser. However alkali metals are very reactive and must be handled in inert atmosphere all through the entire process. If a contamination takes place, it reduces the lithium deposition rate and also the lithium total yield in a not controlled way. An innovative alkali metal dispensing technology has been developed to overcome these problems and ensure OLED alkali metal cathode reliability. The alkali Metal dispenser, called Alkamax, will be able to release up to a few grams of alkali metals (in particular Li and Cs) throughout the adoption of a very stable form of the alkali metal. Lithium, for example, can be evaporated "on demand": the evaporation could be stopped and re-activated without losing alkali metal yield because the metal not yet consumed remains in its stable form. A full characterization of dispensing material, dispenser configuration and dispensing process has been carried out in order to optimize the evaporation and deposition dynamics of alkali metals layers. The study has been performed applying also inside developed simulations tools.

  4. Alkali-Metal Spin Maser.

    PubMed

    Chalupczak, W; Josephs-Franks, P

    2015-07-17

    Quantum measurement is a combination of a read-out and a perturbation of the quantum system. We explore the nonlinear spin dynamics generated by a linearly polarized probe beam in a continuous measurement of the collective spin state in a thermal alkali-metal atomic sample. We demonstrate that the probe-beam-driven perturbation leads, in the presence of indirect pumping, to complete polarization of the sample and macroscopic coherent spin oscillations. As a consequence of the former we report observation of spectral profiles free from collisional broadening. Nonlinear dynamics is studied through exploring its effect on radio frequency as well as spin noise spectra. PMID:26230788

  5. The structure of alkali silicate gel by total scattering methods.

    SciTech Connect

    Benmore, C. J.; Monteiro, P. J. M.; X-Ray Science Division; Univ. of California at Berkeley

    2010-01-01

    The structure of the alkali silicate gel (ASR) collected from the galleries of Furnas Dam in Brazil was determined by a pair distribution function (PDF) analysis of high energy X-ray diffraction data. Since this method is relatively new to concrete structure analysis a detailed introduction on the PDF method is given for glassy SiO{sub 2}. The bulk amorphous structure of the dam material is confirmed as no Bragg peaks are observed in the scattered intensity. The real space results show that the local structure of the amorphous material is similar to kanemite (KHSi{sub 2}O{sub 5}:3H{sub 2}O) however the long range layer structure of the crystal is broken up in the amorphous state, so that ordering only persists of the length scale of a few polyhedra. The silicate layer structure is a much more disordered than predicted by molecular dynamics models. The X-ray results are consistent with the molecular dynamics model of Kirkpatrick et al. (2005) [1] which predicts that most of the water resides in pores within the amorphous network rather than in layers. The total scattering data provide a rigorous basis against which other models may also be tested.

  6. Process for the disposal of alkali metals

    DOEpatents

    Lewis, Leroy C.

    1977-01-01

    Large quantities of alkali metals may be safely reacted for ultimate disposal by contact with a hot concentrated caustic solution. The alkali metals react with water in the caustic solution in a controlled reaction while steam dilutes the hydrogen formed by the reaction to a safe level.

  7. The alkali metals: 200 years of surprises.

    PubMed

    Dye, James L

    2015-03-13

    Alkali metal compounds have been known since antiquity. In 1807, Sir Humphry Davy surprised everyone by electrolytically preparing (and naming) potassium and sodium metals. In 1808, he noted their interaction with ammonia, which, 100 years later, was attributed to solvated electrons. After 1960, pulse radiolysis of nearly any solvent produced solvated electrons, which became one of the most studied species in chemistry. In 1968, alkali metal solutions in amines and ethers were shown to contain alkali metal anions in addition to solvated electrons. The advent of crown ethers and cryptands as complexants for alkali cations greatly enhanced alkali metal solubilities. This permitted us to prepare a crystalline salt of Na(-) in 1974, followed by 30 other alkalides with Na(-), K(-), Rb(-) and Cs(-) anions. This firmly established the -1 oxidation state of alkali metals. The synthesis of alkalides led to the crystallization of electrides, with trapped electrons as the anions. Electrides have a variety of electronic and magnetic properties, depending on the geometries and connectivities of the trapping sites. In 2009, the final surprise was the experimental demonstration that alkali metals under high pressure lose their metallic character as the electrons are localized in voids between the alkali cations to become high-pressure electrides! PMID:25666067

  8. Method of handling radioactive alkali metal waste

    DOEpatents

    Wolson, Raymond D.; McPheeters, Charles C.

    1980-01-01

    Radioactive alkali metal is mixed with particulate silica in a rotary drum reactor in which the alkali metal is converted to the monoxide during rotation of the reactor to produce particulate silica coated with the alkali metal monoxide suitable as a feed material to make a glass for storing radioactive material. Silica particles, the majority of which pass through a 95 mesh screen or preferably through a 200 mesh screen, are employed in this process, and the preferred weight ratio of silica to alkali metal is 7 to 1 in order to produce a feed material for the final glass product having a silica to alkali metal monoxide ratio of about 5 to 1.

  9. Method of handling radioactive alkali metal waste

    DOEpatents

    Wolson, R.D.; McPheeters, C.C.

    Radioactive alkali metal is mixed with particulate silica in a rotary drum reactor in which the alkali metal is converted to the monoxide during rotation of the reactor to produce particulate silica coated with the alkali metal monoxide suitable as a feed material to make a glass for storing radioactive material. Silica particles, the majority of which pass through a 95 mesh screen or preferably through a 200 mesh screen, are employed in this process, and the preferred weight ratio of silica to alkali metal is 7 to 1 in order to produce a feed material for the final glass product having a silica to alkali metal monoxide ratio of about 5 to 1.

  10. Alkali metal for ultraviolet band-pass filter

    NASA Technical Reports Server (NTRS)

    Mardesich, Nick (Inventor); Fraschetti, George A. (Inventor); Mccann, Timothy A. (Inventor); Mayall, Sherwood D. (Inventor); Dunn, Donald E. (Inventor); Trauger, John T. (Inventor)

    1993-01-01

    An alkali metal filter having a layer of metallic bismuth deposited onto the alkali metal is provided. The metallic bismuth acts to stabilize the surface of the alkali metal to prevent substantial surface migration from occurring on the alkali metal, which may degrade optical characteristics of the filter. To this end, a layer of metallic bismuth is deposited by vapor deposition over the alkali metal to a depth of approximately 5 to 10 A. A complete alkali metal filter is described along with a method for fabricating the alkali metal filter.

  11. Integrating Sphere Alkali-Metal Vapor Cells

    NASA Astrophysics Data System (ADS)

    McGuyer, Bart; Ben-Kish, Amit; Jau, Yuan-Yu; Happer, William

    2010-03-01

    An integrating sphere is an optical multi-pass cavity that uses diffuse reflection to increase the optical path length. Typically applied in photometry and radiometry, integrating spheres have previously been used to detect trace gases and to cool and trap alkali-metal atoms. Here, we investigate the potential for integrating spheres to enhance optical absorption in optically thin alkali-metal vapor cells. In particular, we consider the importance of dielectric effects due to a glass container for the alkali-metal vapor. Potential applications include miniature atomic clocks and magnetometers, where multi-passing could reduce the operating temperature and power consumption.

  12. Alkali Metal Handling Practices at NASA MSFC

    NASA Technical Reports Server (NTRS)

    Salvail, Patrick G.; Carter, Robert R.

    2002-01-01

    NASA Marshall Space Flight Center (MSFC) is NASA s principle propulsion development center. Research and development is coordinated and carried out on not only the existing transportation systems, but also those that may be flown in the near future. Heat pipe cooled fast fission cores are among several concepts being considered for the Nuclear Systems Initiative. Marshall Space Flight Center has developed a capability to handle high-purity alkali metals for use in heat pipes or liquid metal heat transfer loops. This capability is a low budget prototype of an alkali metal handling system that would allow the production of flight qualified heat pipe modules or alkali metal loops. The processing approach used to introduce pure alkali metal into heat pipe modules and other test articles are described in this paper.

  13. Effect of silicate modulus and metakaolin incorporation on the carbonation of alkali silicate-activated slags

    SciTech Connect

    Bernal, Susan A.; Mejia de Gutierrez, Ruby; Provis, John L.; Rose, Volker

    2010-06-15

    Accelerated carbonation is induced in pastes and mortars produced from alkali silicate-activated granulated blast furnace slag (GBFS)-metakaolin (MK) blends, by exposure to CO{sub 2}-rich gas atmospheres. Uncarbonated specimens show compressive strengths of up to 63 MPa after 28 days of curing when GBFS is used as the sole binder, and this decreases by 40-50% upon complete carbonation. The final strength of carbonated samples is largely independent of the extent of metakaolin incorporation up to 20%. Increasing the metakaolin content of the binder leads to a reduction in mechanical strength, more rapid carbonation, and an increase in capillary sorptivity. A higher susceptibility to carbonation is identified when activation is carried out with a lower solution modulus (SiO{sub 2}/Na{sub 2}O ratio) in metakaolin-free samples, but this trend is reversed when metakaolin is added due to the formation of secondary aluminosilicate phases. High-energy synchrotron X-ray diffractometry of uncarbonated paste samples shows that the main reaction products in alkali-activated GBFS/MK blends are C-S-H gels, and aluminosilicates with a zeolitic (gismondine) structure. The main crystalline carbonation products are calcite in all samples and trona only in samples containing no metakaolin, with carbonation taking place in the C-S-H gels of all samples, and involving the free Na{sup +} present in the pore solution of the metakaolin-free samples. Samples containing metakaolin do not appear to have the same availability of Na{sup +} for carbonation, indicating that this is more effectively bound in the presence of a secondary aluminosilicate gel phase. It is clear that claims of exceptional carbonation resistance in alkali-activated binders are not universally true, but by developing a fuller mechanistic understanding of this process, it will certainly be possible to improve performance in this area.

  14. Alkali metal crystalline polymer electrolytes.

    PubMed

    Zhang, Chuhong; Gamble, Stephen; Ainsworth, David; Slawin, Alexandra M Z; Andreev, Yuri G; Bruce, Peter G

    2009-07-01

    Polymer electrolytes have been studied extensively because uniquely they combine ionic conductivity with solid yet flexible mechanical properties, rendering them important for all-solid-state devices including batteries, electrochromic displays and smart windows. For some 30 years, ionic conductivity in polymers was considered to occur only in the amorphous state above Tg. Crystalline polymers were believed to be insulators. This changed with the discovery of Li(+) conductivity in crystalline poly(ethylene oxide)(6):LiAsF(6). However, new crystalline polymer electrolytes have proved elusive, questioning whether the 6:1 complex has particular structural features making it a unique exception to the rule that only amorphous polymers conduct. Here, we demonstrate that ionic conductivity in crystalline polymers is not unique to the 6:1 complex by reporting several new crystalline polymer electrolytes containing different alkali metal salts (Na(+), K(+) and Rb(+)), including the best conductor poly(ethylene oxide)(8):NaAsF(6) discovered so far, with a conductivity 1.5 orders of magnitude higher than poly(ethylene oxide)(6):LiAsF(6). These are the first crystalline polymer electrolytes with a different composition and structures to that of the 6:1 Li(+) complex. PMID:19543313

  15. Alkali metal intercalates of molybdenum disulfide.

    NASA Technical Reports Server (NTRS)

    Somoano, R. B.; Hadek, V.; Rembaum, A.

    1973-01-01

    Study of some of the physicochemical properties of compounds obtained by subjecting natural molybdenite and single crystals of molybdenum disulfide grown by chemical vapor transport to intercalation with the alkali group of metals (Li, Na, K, Rb, and Cs) by means of the liquid ammonia technique. Reported data and results include: (1) the intercalation of the entire alkali metal group, (2) stoichiometries and X-ray data on all of the compounds, and (3) superconductivity data for all the intercalation compounds.

  16. Alkali-metal intercalation in carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Béguin, F.; Duclaux, L.; Méténier, K.; Frackowiak, E.; Salvetat, J. P.; Conard, J.; Bonnamy, S.; Lauginie, P.

    1999-09-01

    We report on successful intercalation of multiwall (MWNT) and single wall (SWNT) carbon nanotubes with alkali metals by electrochemical and vapor phase reactions. A LiC10 compound was produced by full electrochemical reduction of MWNT. KC8 and CsC8-MWNT first stage derivatives were synthesized in conditions of alkali vapor saturation. Their identity periods and the 2×2 R 0° alkali superlattice are comparable to their parent graphite compounds. The dysonian shape of KC8 EPR line and the temperature-independent Pauli susceptibility are both characteristic of a metallic behavior, which was confirmed by 13C NMR anisotropic shifts. Exposure of SWNT bundles to alkali vapor led to an increase of the pristine triangular lattice from 1.67 nm to 1.85 nm and 1.87 nm for potassium and rubidium, respectively.

  17. A Calculation of Spatial Range of Colloidal Silicic Acid Deposited Downstream from the Alkali Front

    NASA Astrophysics Data System (ADS)

    Niibori, Yuichi; Iijima, Kazuki; Tamura, Naoyuki; Mimura, Hitoshi

    A high alkali domain spreads out due to the use of cement materials for the construction of the repository of radioactive wastes. Sudden change of pH at this alkali front produces colloidal silicic acid (polymeric silicic acid) in addition to the deposition of supersaturated monomeric silicic acid onto the fracture surface of flow-pathway. The colloidal silicic acid also deposits with relatively small rate-constant in the co-presence of solid phase. Once the flow-path surface is covered with the amorphous silica, the surface seriously degrades the sorption behavior of radionuclides (RNs). Therefore, so far, the authors have examined the deposition rates of supersaturated silicic acid. This study summarized the deposition rate-constants defined by the first-order reaction equation under various conditions of co-presence of amorphous silica powder. Then, using the smallest rate-constant (1.0×10-12 m/s in the co-presence of calcium ions of 1 mM) and a simulation code, COLFRAC-MRL, the spatial range of colloidal silicic acid deposited downstream from the alkali front was estimated. The results suggested the clogging caused by the deposition of colloidal silicic acid in flow-path. The altered spatial range in the flow-path was limited to around 30 m in fracture and to several centimeters in rock matrix.

  18. SAFE Alkali Metal Heat Pipe Reliability

    NASA Astrophysics Data System (ADS)

    Reid, Robert S.

    2003-01-01

    Alkali metal heat pipes are among the best understood and tested of components for first generation space fission reactors. A flight reactor will require production of a hundred or more heat pipes with assured reliability over a number of years. To date, alkali metal heat pipes have been built mostly in low budget development environments with little formal quality assurance. Despite this, heat pipe test samples suggest that high reliability can be achieved with the care justified for space flight qualification. Fabrication procedures have been established that, if consistently applied, ensure long-term trouble-free heat pipe operation. Alkali metal heat pipes have been successfully flight tested in micro gravity and also have been shown capable of multi-year operation with no evidence of sensitivity to fast neutron fluence up to 1023 n/cm2. This represents 50 times the fluence of the proposed Safe Affordable Fission Engine (SAFE-100) heat pipe reactor core.

  19. Alkali metal vapors - Laser spectroscopy and applications

    NASA Technical Reports Server (NTRS)

    Stwalley, W. C.; Koch, M. E.

    1980-01-01

    The paper examines the rapidly expanding use of lasers for spectroscopic studies of alkali metal vapors. Since the alkali metals (lithium, sodium, potassium, rubidium and cesium) are theoretically simple ('visible hydrogen'), readily ionized, and strongly interacting with laser light, they represent ideal systems for quantitative understanding of microscopic interconversion mechanisms between photon (e.g., solar or laser), chemical, electrical and thermal energy. The possible implications of such understanding for a wide variety of practical applications (sodium lamps, thermionic converters, magnetohydrodynamic devices, new lasers, 'lithium waterfall' inertial confinement fusion reactors, etc.) are also discussed.

  20. Recovery of alkali metal constituents from catalytic coal conversion residues

    DOEpatents

    Soung, W.Y.

    In a coal gasification operation (32) or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles by contacting them with water or an aqueous solution to remove water-soluble alkali metal constituents and produce an aqueous solution enriched in said constituents. The aqueous solution thus produced is then contacted with carbon dioxide to precipitate silicon constituents, the pH of the resultant solution is increased, preferably to a value in the range between about 12.5 and about 15.0, and the solution of increased pH is evaporated to increase the alkali metal concentration. The concentrated aqueous solution is then recycled to the conversion process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst.

  1. Salts of alkali metal anions and process of preparing same

    DOEpatents

    Dye, James L.; Ceraso, Joseph M.; Tehan, Frederick J.; Lok, Mei Tak

    1978-01-01

    Compounds of alkali metal anion salts of alkali metal cations in bicyclic polyoxadiamines are disclosed. The salts are prepared by contacting an excess of alkali metal with an alkali metal dissolving solution consisting of a bicyclic polyoxadiamine in a suitable solvent, and recovered by precipitation. The salts have a gold-color crystalline appearance and are stable in a vacuum at -10.degree. C. and below.

  2. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for...

  3. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for...

  4. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for...

  5. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for...

  6. 40 CFR 721.4660 - Alcohol, alkali metal salt.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alcohol, alkali metal salt. 721.4660... Substances § 721.4660 Alcohol, alkali metal salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance generically identified as alcohol, alkali metal salt (PMN P-91-151)...

  7. 40 CFR 721.4660 - Alcohol, alkali metal salt.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alcohol, alkali metal salt. 721.4660... Substances § 721.4660 Alcohol, alkali metal salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance generically identified as alcohol, alkali metal salt (PMN P-91-151)...

  8. 40 CFR 721.4660 - Alcohol, alkali metal salt.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alcohol, alkali metal salt. 721.4660... Substances § 721.4660 Alcohol, alkali metal salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance generically identified as alcohol, alkali metal salt (PMN P-91-151)...

  9. 40 CFR 721.4660 - Alcohol, alkali metal salt.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alcohol, alkali metal salt. 721.4660... Substances § 721.4660 Alcohol, alkali metal salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance generically identified as alcohol, alkali metal salt (PMN P-91-151)...

  10. 40 CFR 721.4660 - Alcohol, alkali metal salt.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alcohol, alkali metal salt. 721.4660... Substances § 721.4660 Alcohol, alkali metal salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance generically identified as alcohol, alkali metal salt (PMN P-91-151)...

  11. Alkali-metal azides interacting with metal-organic frameworks.

    PubMed

    Armata, Nerina; Cortese, Remedios; Duca, Dario; Triolo, Roberto

    2013-01-14

    Interactions between alkali-metal azides and metal-organic framework (MOF) derivatives, namely, the first and third members of the isoreticular MOF (IRMOF) family, IRMOF-1 and IRMOF-3, are studied within the density functional theory (DFT) paradigm. The investigations take into account different models of the selected IRMOFs. The mutual influence between the alkali-metal azides and the π rings or Zn centers of the involved MOF derivatives are studied by considering the interactions both of the alkali-metal cations with model aromatic centers and of the alkali-metal azides with distinct sites of differently sized models of IRMOF-1 and IRMOF-3. Several exchange and correlation functionals are employed to calculate the corresponding interaction energies. Remarkably, it is found that, with increasing alkali-metal atom size, the latter decrease for cations interacting with the π-ring systems and increase for the azides interacting with the MOF fragments. The opposite behavior is explained by stabilization effects on the azide moieties and determined by the Zn atoms, which constitute the inorganic vertices of the IRMOF species. Larger cations can, in fact, coordinate more efficiently to both the aromatic center and the azide anion, and thus stabilizing bridging arrangements of the azide between one alkali-metal and two Zn atoms in an η(2) coordination mode are more favored. PMID:23161861

  12. Removal of Retired Alkali Metal Test Systems

    SciTech Connect

    BREHM, W.F.

    2003-01-01

    This paper describes the successful effort to remove alkali metals, alkali metal residues, and piping and structures from retired non-radioactive test systems on the Hanford Site. These test systems were used between 1965 and 1982 to support the Fast Flux Test Facility and the Liquid Metal Fast Breeder Reactor Program. A considerable volume of sodium and sodium-potassium alloy (NaK) was successfully recycled to the commercial sector; structural material and electrical material such as wiring was also recycled. Innovative techniques were used to safely remove NaK and its residues from a test system that could not be gravity-drained. The work was done safely, with no environmental issues or significant schedule delays.

  13. Removal of Retired Alkali Metal Test Systems

    SciTech Connect

    Brehm, W. F.; Church, W. R.; Biglin, J. W.

    2003-02-26

    This paper describes the successful effort to remove alkali metals, alkali metal residues, and piping and structures from retired non-radioactive test systems on the Hanford Site. These test systems were used between 1965 and 1982 to support the Fast Flux Test Facility and the Liquid Metal Fast Breeder Reactor Program. A considerable volume of sodium and sodium-potassium alloy (NaK) was successfully recycled to the commercial sector; structural material and electrical material such as wiring was also recycled. Innovative techniques were used to safely remove NaK and its residues from a test system that could not be gravity-drained. The work was done safely, with no environmental issues or significant schedule delays.

  14. Alkali-Activated Aluminium-Silicate Composites as Insulation Materials for Industrial Application

    NASA Astrophysics Data System (ADS)

    Dembovska, L.; Bajare, D.; Pundiene, I.; Bumanis, G.

    2015-11-01

    The article reports on the study of thermal stability of alkali-activated aluminium- silicate composites (ASC) at temperature 800-1100°C. ASC were prepared by using calcined kaolinite clay, aluminium scrap recycling waste, lead-silicate glass waste and quartz sand. As alkali activator, commercial sodium silicate solution modified with an addition of sodium hydroxide was used. The obtained alkali activation solution had silica modulus Ms=1.67. Components of aluminium scrap recycling waste (aluminium nitride (AlN) and iron sulphite (FeSO3)) react in the alkali media and create gases - ammonia and sulphur dioxide, which provide the porous structure of the material [1]. Changes in the chemical composition of ASC during heating were identified and quantitatively analysed by using DTA/TG, dimension changes during the heating process were determined by using HTOM, pore microstructure was examined by SEM, and mineralogical composition of ASC was determined by XRD. The density of ASC was measured in accordance with EN 1097-7. ASC with density around 560 kg/m3 and heat resistance up to 1100°C with shrinkage less than 5% were obtained. The intended use of this material is the application as an insulation material for industrial purposes at elevated temperatures.

  15. Alkali metal recovery from carbonaceous material conversion process

    DOEpatents

    Sharp, David W.; Clavenna, LeRoy R.; Gorbaty, Martin L.; Tsou, Joe M.

    1980-01-01

    In a coal gasification operation or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein solid particles containing alkali metal residues are produced in the gasifier or similar reaction zone, alkali metal constitutents are recovered from the particles by withdrawing and passing the particles from the reaction zone to an alkali metal recovery zone in the substantial absence of molecular oxygen and treating the particles in the recovery zone with water or an aqueous solution in the substantial absence of molecular oxygen. The solution formed by treating the particles in the recovery zone will contain water-soluble alkali metal constituents and is recycled to the conversion process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst. Preventing contact of the particles with oxygen as they are withdrawn from the reaction zone and during treatment in the recovery zone avoids the formation of undesirable alkali metal constituents in the aqueous solution produced in the recovery zone and insures maximum recovery of water-soluble alkali metal constituents from the alkali metal residues.

  16. Alkali Metal Heat Pipe Life Issues

    NASA Technical Reports Server (NTRS)

    Reid, Robert S.

    2004-01-01

    One approach to space fission power system design is predicated on the use of alkali metal heat pipes, either as radiator elements, thermal management components, or as part of the core primary heat-transfer system. This synopsis characterizes long-life core heat pipes. References are included where more detailed information can be found. Specifics shown here are for demonstrational purposes and do not necessarily reflect current Project Prometheus point designs.

  17. Alkali metal protective garment and composite material

    SciTech Connect

    Ballif, J.L.; Yuan, W.W.

    1980-09-16

    A protective garment and composite material providing satisfactory heat resistance and physical protection for articles and personnel exposed to hot molten alkali metals, such as sodium are described. Physical protection is provided by a continuous layer of nickel foil. Heat resistance is provided by an underlying backing layer of thermal insulation. Overlying outer layers of fireproof woven ceramic fibers are used to protect the foil during storage and handling.

  18. Alkali metal protective garment and composite material

    SciTech Connect

    Ballif, III, John L.; Yuan, Wei W.

    1980-01-01

    A protective garment and composite material providing satisfactory heat resistance and physical protection for articles and personnel exposed to hot molten alkali metals, such as sodium. Physical protection is provided by a continuous layer of nickel foil. Heat resistance is provided by an underlying backing layer of thermal insulation. Overlying outer layers of fireproof woven ceramic fibers are used to protect the foil during storage and handling.

  19. Method for the safe disposal of alkali metal

    DOEpatents

    Johnson, Terry R.

    1977-01-01

    Alkali metals such as those employed in liquid metal coolant systems can be safely reacted to form hydroxides by first dissolving the alkali metal in relatively inert metals such as lead or bismuth. The alloy thus formed is contacted with a molten salt including the alkali metal hydroxide and possibly the alkali metal carbonate in the presence of oxygen. This oxidizes the alkali metal to an oxide which is soluble within the molten salt. The salt is separated and contacted with steam or steam-CO.sub.2 mixture to convert the alkali metal oxide to the hydroxide. These reactions can be conducted with minimal hydrogen evolution and with the heat of reaction distributed between the several reaction steps.

  20. Electrochemical devices utilizing molten alkali metal electrode-reactant

    DOEpatents

    Hitchcock, D.C.; Mailhe, C.C.; De Jonghe, L.C.

    1985-07-10

    Electrochemical cells are provided with a reactive metal to reduce the oxide of the alkali metal electrode-reactant. Cells employing a molten alkali metal electrode, e.g., sodium, in contact with a ceramic electrolyte, which is a conductor of the ions of the alkali metal forming the electrode, exhibit a lower resistance when a reactive metal, e.g., vanadium, is allowed to react with and reduce the alkali metal oxide. Such cells exhibit less degradation of the electrolyte and of the glass seals often used to joining the electrolyte to the other components of the cell under cycling conditions.

  1. Electrochemical devices utilizing molten alkali metal electrode-reactant

    DOEpatents

    Hitchcock, David C.; Mailhe, Catherine C.; De Jonghe, Lutgard C.

    1986-01-01

    Electrochemical cells are provided with a reactive metal to reduce the oxide of the alkali metal electrode-reactant. Cells employing a molten alkali metal electrode, e.g., sodium, in contact with a ceramic electrolyte, which is a conductor of the ions of the alkali metal forming the electrode, exhibit a lower resistance when a reactive metal, e.g., vanadium, is allowed to react with and reduce the alkali metal oxide. Such cells exhibit less degradation of the electrolyte and of the glass seals often used to joining the electrolyte to the other components of the cell under cycling conditions.

  2. Heat capacity, glass transition temperature, size of cooperatively rearranging regions, and network connectivity of sodium silicate and alkali borate glasses

    SciTech Connect

    Borisova, N.V.; Ushakov, V.M.; Shultz, M.M.

    1994-07-01

    The radius of cooperatively rearranging domains at the glass transition in sodium silicate glasses and the number of bridging oxygen atoms in these domains are assessed within the framework of the kinetic theory of thermal fluctuations. The tendencies of the heat capacity, T{sub g}, and the cooperative rearrangement scale with the alkali oxide concentration in sodium silicate and alkali borate glasses are compared. The points of similarity and distinctions between them are revealed.

  3. Developments in alkali-metal atomic magnetometry

    NASA Astrophysics Data System (ADS)

    Seltzer, Scott Jeffrey

    Alkali-metal magnetometers use the coherent precession of polarized atomic spins to detect and measure magnetic fields. Recent advances have enabled magnetometers to become competitive with SQUIDs as the most sensitive magnetic field detectors, and they now find use in a variety of areas ranging from medicine and NMR to explosives detection and fundamental physics research. In this thesis we discuss several developments in alkali-metal atomic magnetometry for both practical and fundamental applications. We present a new method of polarizing the alkali atoms by modulating the optical pumping rate at both the linear and quadratic Zeeman resonance frequencies. We demonstrate experimentally that this method enhances the sensitivity of a potassium magnetometer operating in the Earth's field by a factor of 4, and we calculate that it can reduce the orientation-dependent heading error to less than 0.1 nT. We discuss a radio-frequency magnetometer for detection of oscillating magnetic fields with sensitivity better than 0.2 fT/ Hz , which we apply to the observation of nuclear magnetic resonance (NMR) signals from polarized water, as well as nuclear quadrupole resonance (NQR) signals from ammonium nitrate. We demonstrate that a spin-exchange relaxation-free (SERF) magnetometer can measure all three vector components of the magnetic field in an unshielded environment with comparable sensitivity to other devices. We find that octadecyltrichlorosilane (OTS) acts as an anti-relaxation coating for alkali atoms at temperatures below 170°C, allowing them to collide with a glass surface up to 2,000 times before depolarizing, and we present the first demonstration of high-temperature magnetometry with a coated cell. We also describe a reusable alkali vapor cell intended for the study of interactions between alkali atoms and surface coatings. Finally, we explore the use of a cesium-xenon SERF comagnetometer for a proposed measurement of the permanent electric dipole moments (EDMs

  4. Water and magmas: insights about the water solution mechanisms in alkali silicate melts from infrared, Raman, and 29Si solid-state NMR spectroscopies

    NASA Astrophysics Data System (ADS)

    Le Losq, Charles; Mysen, Bjorn O.; Cody, George D.

    2015-12-01

    Degassing of water during the ascent of hydrous magma in a volcanic edifice produces dramatic changes in the magma density and viscosity. This can profoundly affect the dynamics of volcanic eruptions. The water exsolution history, in turn, is driven by the water solubility and solution mechanisms in the silicate melt. Previous studies pointed to dissolved water in silicate glasses and melts existing as molecules (H2Omol species) and hydroxyl groups, OH. These latter OH groups commonly are considered bonded to Si4+ but may form other bonds, such as with alkali or alkaline-earth cations, for instance. Those forms of bonding influence the structure of hydrous melts in different ways and, therefore, their properties. As a result, exsolution of water from magmas may have different eruptive consequences depending on the initial bonding mechanisms of the dissolved water. However, despite their importance, the solution mechanisms of water in silicate melts are not clear. In particular, how chemical composition of melts affects water solubility and solution mechanism is not well understood. In the present experimental study, components of such information are reported via determination of how water interacts with the cationic network of alkali (Li, Na, and K) silicate quenched melts. Results from 29Si single-pulse magic-angle spinning nuclear magnetic resonance (29Si SP MAS NMR), infrared, and Raman spectroscopies show that decreasing the ionic radius of alkali metal cation in silicate melts results in decreasing fraction of water dissolved as OH groups. The nature of OH bonding also changes as the alkali ionic radius changes. Therefore, as the speciation and bonding of water controls the degree of polymerization of melts, water will have different effects on the transport properties of silicate melts depending on their chemical composition. This conclusion, in turn, may affect volcanic phenomena related to the viscous relaxation of hydrous magmas, such as for instance the

  5. 40 CFR 721.10495 - Metal silicate (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Metal silicate (generic). 721.10495... Substances § 721.10495 Metal silicate (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as metal silicate (PMN P-05-634) is subject...

  6. 40 CFR 721.10495 - Metal silicate (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Metal silicate (generic). 721.10495... Substances § 721.10495 Metal silicate (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as metal silicate (PMN P-05-634) is subject...

  7. Thermal history effects on electrical relaxation and conductivity for potassium silicate glass with low alkali concentrations

    NASA Technical Reports Server (NTRS)

    Angel, Paul W.; Hann, Raiford E.; Cooper, Alfred R.

    1993-01-01

    Electrical response measurements from 10 Hz to 100 kHz between 120 and 540 C were made on potassium-silicate glasses with alkali oxide contents of 2, 3, 5 and 10 mol percent. Low alkali content glasses were chosen in order to try to reduce the Coulombic interactions between alkali ions to the point that frozen structural effects from the glass could be observed. Conductivity and electrical relaxation responses for both annealed and quenched glasses of the same composition were compared. Lower DC conductivity (sigma(sub DC)) activation energies were measured for the quenched compared to the annealed glasses. The two glasses with the lowest alkali contents exhibited a non-Arrhenius concave up curvature in the log(sigma(sub DC)) against 1/T plots, which decreased upon quenching. A sharp decrease in sigma(sub DC) was observed for glasses containing K2O concentrations of 5 mol percent or less. The log modulus loss peak (M'') maximum frequency plots against 1/T all showed Arrhenius behavior for both annealed and quenched samples. The activation energies for these plots closely agreed with the sigma(sub DC) activation energies. A sharp increase in activation energy was observed for both series as the potassium oxide concentration decreased. Changes in the electrical response are attributed to structural effects due to different alkali concentrations. Differences between the annealed and quenched response are linked to a change in the distribution of activation energies (DAE).

  8. Electrodes For Alkali-Metal Thermoelectric Converters

    NASA Technical Reports Server (NTRS)

    Williams, Roger M.; Wheeler, Bob L.; Jeffries-Nakamura, Barbara; Lamb, James L.; Bankston, C. Perry; Cole, Terry

    1989-01-01

    Combination of thin, porous electrode and overlying collector grid reduces internal resistance of alkali-metal thermoelectric converter cell. Low resistance of new electrode and grid boosts power density nearly to 1 W/cm2 of electrode area at typical operating temperatures of 1,000 to 1,300 K. Conductive grid encircles electrode film on alumina tube. Bus wire runs along tube to collect electrical current from grid. Such converters used to transform solar, nuclear, and waste heat into electric power.

  9. Cathode architectures for alkali metal / oxygen batteries

    SciTech Connect

    Visco, Steven J; Nimon, Vitaliy; De Jonghe, Lutgard C; Volfkovich, Yury; Bograchev, Daniil

    2015-01-13

    Electrochemical energy storage devices, such as alkali metal-oxygen battery cells (e.g., non-aqueous lithium-air cells), have a cathode architecture with a porous structure and pore composition that is tailored to improve cell performance, especially as it pertains to one or more of the discharge/charge rate, cycle life, and delivered ampere-hour capacity. A porous cathode architecture having a pore volume that is derived from pores of varying radii wherein the pore size distribution is tailored as a function of the architecture thickness is one way to achieve one or more of the aforementioned cell performance improvements.

  10. Superconductivity in alkali metal intercalated iron selenides.

    PubMed

    Krzton-Maziopa, A; Svitlyk, V; Pomjakushina, E; Puzniak, R; Conder, K

    2016-07-27

    Alkali metal intercalated iron selenide superconductors A x Fe2-y Se2 (where A  =  K, Rb, Cs, Tl/K, and Tl/Rb) are characterized by several unique properties, which were not revealed in other superconducting materials. The compounds crystallize in overall simple layered structure with FeSe layers intercalated with alkali metal. The structure turned out to be pretty complex as the existing Fe-vacancies order below ~550 K, which further leads to an antiferromagnetic ordering with Néel temperature fairly above room temperature. At even lower temperatures a phase separation is observed. While one of these phases stays magnetic down to the lowest temperatures the second is becoming superconducting below ~30 K. All these effects give rise to complex relationships between the structure, magnetism and superconductivity. In particular the iron vacancy ordering, linked with a long-range magnetic order and a mesoscopic phase separation, is assumed to be an intrinsic property of the system. Since the discovery of superconductivity in those compounds in 2010 they were investigated very extensively. Results of the studies conducted using a variety of experimental techniques and performed during the last five years were published in hundreds of reports. The present paper reviews scientific work concerning methods of synthesis and crystal growth, structural and superconducting properties as well as pressure investigations. PMID:27248118

  11. Superconductivity in alkali metal intercalated iron selenides

    NASA Astrophysics Data System (ADS)

    Krzton-Maziopa, A.; Svitlyk, V.; Pomjakushina, E.; Puzniak, R.; Conder, K.

    2016-07-01

    Alkali metal intercalated iron selenide superconductors A x Fe2‑y Se2 (where A  =  K, Rb, Cs, Tl/K, and Tl/Rb) are characterized by several unique properties, which were not revealed in other superconducting materials. The compounds crystallize in overall simple layered structure with FeSe layers intercalated with alkali metal. The structure turned out to be pretty complex as the existing Fe-vacancies order below ~550 K, which further leads to an antiferromagnetic ordering with Néel temperature fairly above room temperature. At even lower temperatures a phase separation is observed. While one of these phases stays magnetic down to the lowest temperatures the second is becoming superconducting below ~30 K. All these effects give rise to complex relationships between the structure, magnetism and superconductivity. In particular the iron vacancy ordering, linked with a long-range magnetic order and a mesoscopic phase separation, is assumed to be an intrinsic property of the system. Since the discovery of superconductivity in those compounds in 2010 they were investigated very extensively. Results of the studies conducted using a variety of experimental techniques and performed during the last five years were published in hundreds of reports. The present paper reviews scientific work concerning methods of synthesis and crystal growth, structural and superconducting properties as well as pressure investigations.

  12. Heat pipes containing alkali metal working fluid

    NASA Technical Reports Server (NTRS)

    Morris, J. F. (Inventor)

    1981-01-01

    A technique for improving high temperature evaporation-condensation heat-transfer devices which have important and unique advantage in terrestrial and space energy processing is described. The device is in the form of a heat pipe comprising a sealed container or envelope which contains a capillary wick. The temperature of one end of the heat pipe is raised by the input of heat from an external heat source which is extremely hot and corrosive. A working fluid of a corrosive alkali metal, such as lithium, sodium, or potassium transfers this heat to a heat receiver remote from the heat source. The container and wick are fabricated from a superalloy containing a small percentage of a corrosion inhibiting or gettering element. Lanthanum, scandium, yttrium, thorium, and hafnium are utilized as the alloying metal.

  13. Recovery of alkali metal constituents from catalytic coal conversion residues

    DOEpatents

    Soung, Wen Y.

    1984-01-01

    In a coal gasification operation (32) or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles by contacting them (46, 53, 61, 69) with water or an aqueous solution to remove water-soluble alkali metal constituents and produce an aqueous solution enriched in said constituents. The aqueous solution thus produced is then contacted with carbon dioxide (63) to precipitate silicon constituents, the pH of the resultant solution is increased (81), preferably to a value in the range between about 12.5 and about 15.0, and the solution of increased pH is evaporated (84) to increase the alkali metal concentration. The concentrated aqueous solution is then recycled to the conversion process (86, 18, 17) where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst.

  14. 40 CFR 721.4740 - Alkali metal nitrites.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... defined in 40 CFR 721.3) containing amines. (b) ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkali metal nitrites. 721.4740... Substances § 721.4740 Alkali metal nitrites. (a) Chemical substances and significant new use subject...

  15. 40 CFR 721.4740 - Alkali metal nitrites.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... defined in 40 CFR 721.3) containing amines. (b) ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkali metal nitrites. 721.4740... Substances § 721.4740 Alkali metal nitrites. (a) Chemical substances and significant new use subject...

  16. 40 CFR 721.4740 - Alkali metal nitrites.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... defined in 40 CFR 721.3) containing amines. (b) ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkali metal nitrites. 721.4740... Substances § 721.4740 Alkali metal nitrites. (a) Chemical substances and significant new use subject...

  17. 40 CFR 721.4740 - Alkali metal nitrites.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... defined in 40 CFR 721.3) containing amines. (b) ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkali metal nitrites. 721.4740... Substances § 721.4740 Alkali metal nitrites. (a) Chemical substances and significant new use subject...

  18. Self-discharge in bimetallic cells containing alkali metal

    NASA Technical Reports Server (NTRS)

    Foster, M. S.; Hesson, J. C.; Shimotake, H.

    1969-01-01

    Theoretical analysis of thermally regenerative bimetallic cells with alkali metal anodes shows a relation between the current drawn and the rate of discharge under open-circuit conditions. The self-discharge rate of the cell is due to the dissolution and ionization of alkali metal atoms in the fused-salt electrolyte

  19. COMPLEX FLUORIDES OF PLUTONIUM AND AN ALKALI METAL

    DOEpatents

    Seaborg, G.T.

    1960-08-01

    A method is given for precipitating alkali metal plutonium fluorides. such as KPuF/sub 5/, KPu/sub 2/F/sub 9/, NaPuF/sub 5/, and RbPuF/sub 5/, from an aqueous plutonium(IV) solution by adding hydrogen fluoride and alkali-metal- fluoride.

  20. 40 CFR 721.4740 - Alkali metal nitrites.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.4740 Alkali metal nitrites. (a) Chemical substances and significant new use subject to reporting. (1) The category of chemical substances which are nitrites of the alkali metals (Group IA in...

  1. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkali metal alkyl...

  2. The structure of metallic complexes of polyacetylene with alkali metals

    NASA Astrophysics Data System (ADS)

    Baughman, R. H.; Murthy, N. S.; Miller, G. G.

    1983-07-01

    The crystal structures of sodium, potassium, rubidium, and cesium doped polyacetylene have been determined using crystal packing and x-ray diffraction analyses. Each of these metallic complexes is tetragonal, with the polyacetylene chains forming a host lattice in which the alkali metal ions are present in channels. Lithium appears to be too small to stabilize the channel structure and an amorphous structure is observed. Predicted unit cell parameters and x-ray diffraction intensities are in agreement with observed values. Similarities with the alkali metal doped graphite suggest that hybridization between carbon pz orbitals and metal s orbitals occurs. Such hybridization is expected to result in a high conductivity component normal to the chain direction. On the other hand, direct overlap between polymer chains appears small, since alkali metal columns separate polymer chains. Compositions calculated for the channel structures (from meridional diffraction spacings, the intensity of equatorial diffraction lines, measured volume expansion, and distances in model complexes) all range from y=0.12 to 0.18 for (CHMy)x, where M is sodium, potassium, rubidium, or cesium.

  3. Silicate species of water glass and insights for alkali-activated green cement

    SciTech Connect

    Jansson, Helén; Bernin, Diana; Ramser, Kerstin

    2015-06-15

    Despite that sodium silicate solutions of high pH are commonly used in industrial applications, most investigations are focused on low to medium values of pH. Therefore we have investigated such solutions in a broad modulus range and up to high pH values (∼14) by use of infrared (IR) spectroscopy and silicon nuclear magnetic resonance ({sup 29}Si-NMR). The results show that the modulus dependent pH value leads to more or less charged species, which affects the configurations of the silicate units. This in turn, influences the alkali-activation process of low CO{sub 2} footprint cements, i.e. materials based on industrial waste or by-products.

  4. Silicate species of water glass and insights for alkali-activated green cement

    NASA Astrophysics Data System (ADS)

    Jansson, Helén; Bernin, Diana; Ramser, Kerstin

    2015-06-01

    Despite that sodium silicate solutions of high pH are commonly used in industrial applications, most investigations are focused on low to medium values of pH. Therefore we have investigated such solutions in a broad modulus range and up to high pH values (˜14) by use of infrared (IR) spectroscopy and silicon nuclear magnetic resonance (29Si-NMR). The results show that the modulus dependent pH value leads to more or less charged species, which affects the configurations of the silicate units. This in turn, influences the alkali-activation process of low CO2 footprint cements, i.e. materials based on industrial waste or by-products.

  5. Electrochemical cell utilizing molten alkali metal electrode-reactant

    DOEpatents

    Virkar, Anil V.; Miller, Gerald R.

    1983-11-04

    An improved electrochemical cell comprising an additive-modified molten alkali metal electrode-reactant and/or electrolyte is disclosed. Various electrochemical cells employing a molten alkali metal, e.g., sodium, electrode in contact with a cationically conductive ceramic membrane experience a lower resistance and a lower temperature coefficient of resistance whenever small amounts of selenium are present at the interface of the electrolyte and the molten alkali metal. Further, cells having small amounts of selenium present at the electrolyte-molten metal interface exhibit less degradation of the electrolyte under long term cycling conditions.

  6. Metal-Silicate Segregation in Asteroidal Meteorites

    NASA Technical Reports Server (NTRS)

    Herrin, Jason S.; Mittlefehldt, D. W.

    2006-01-01

    A fundamental process of planetary differentiation is the segregation of metal-sulfide and silicate phases, leading eventually to the formation of a metallic core. Asteroidal meteorites provide a glimpse of this process frozen in time from the early solar system. While chondrites represent starting materials, iron meteorites provide an end product where metal has been completely concentrated in a region of the parent asteroid. A complimentary end product is seen in metal-poor achondrites that have undergone significant igneous processing, such as angrites, HED's and the majority of aubrites. Metal-rich achondrites such as acapulcoite/lodranites, winonaites, ureilites, and metal-rich aubrites may represent intermediate stages in the metal segregation process. Among these, acapulcoite-lodranites and ureilites are examples of primary metal-bearing mantle restites, and therefore provide an opportunity to observe the metal segregation process that was captured in progress. In this study we use bulk trace element compositions of acapulcoites-lodranites and ureilites for this purpose.

  7. Crystal Structures of Three Framework Alkali Metal Uranyl Phosphate Hydrates

    NASA Astrophysics Data System (ADS)

    Locock, Andrew J.; Burns, Peter C.

    2002-08-01

    Three homeotypic hydrated alkali metal uranyl phosphates, A2(UO 2)[(UO 2)(PO 4)] 4(H 2O) 2, A=Cs ( CsUP), Rb ( RbUP), K ( KUP), were synthesized by hydrothermal methods. Intensity data were collected at room temperature using Mo Kα radiation and a CCD-based area detector. Their crystal structures were solved by Patterson ( CsUP) and direct ( RbUP, KUP) methods and refined by full-matrix least-squares techniques to agreement indices ( CsUP, RbUP, KUP) w R2=0.048, 0.230, 0.072 for all data, and R1=0.023, 0.078, 0.038 calculated for 5338, 4738, 4514 unique observed reflections (∣ Fo∣≥4 σF), respectively. The compound CsUP is orthorhombic, space group Cmc2 1, Z=4, a=14.854(1), b=13.879(1), c=12.987(1) Å, V=2677.5(3) Å 3. Both RbUP and KUP are monoclinic, space group Cm, but are presented in the unconventional pseudo-orthorhombic space group Fm11 to facilitate comparison with CsUP and to allow a model for RbUP that includes the effects of pseudo-merohedral twinning. RbUP is monoclinic, space group Fm11, Z=4, a=15.72(2), b=13.84(1), c=13.05(1) Å, α=90.39°(2), V=2839(5) Å 3; KUP is monoclinic, space group Fm11, Z=4, a=15.257(1), b=13.831(1), c=13.007(1) Å, α=91.760°(1), V=2743.4(3) Å 3. The structures consist of sheets of phosphate tetrahedra and uranyl pentagonal bipyramids, with composition [(UO 2)(PO 4)] -, that are topologically identical to the uranyl silicate sheets in uranophane-beta. These sheets are connected by a uranyl pentagonal bipyramid in the interlayer that shares corners with two phosphate tetrahedra on each of two adjacent sheets and whose fifth equatorial vertex is an H 2O group, resulting in an open framework with alkali metal cations in the larger cavities of the structures. Where CsUP and RbUP have two alkali metal positions and a H 2O group in these cavities, KUP has four K atoms and two H 2O groups, all of which are partially occupied, in the interstitial sites.

  8. Alkali metal-refractory metal biphase electrode for AMTEC

    NASA Technical Reports Server (NTRS)

    Williams, Roger M. (Inventor); Bankston, Clyde P. (Inventor); Cole, Terry (Inventor); Khanna, Satish K. (Inventor); Jeffries-Nakamura, Barbara (Inventor); Wheeler, Bob L. (Inventor)

    1989-01-01

    An electrode having increased output with slower degradation is formed of a film applied to a beta-alumina solid electrolyte (BASE). The film comprises a refractory first metal M.sup.1 such as a platinum group metal, suitably platinum or rhodium, capable of forming a liquid or a strong surface adsorption phase with sodium at the operating temperature of an alkali metal thermoelectric converter (AMTEC) and a second refractory metal insoluble in sodium or the NaM.sup.1 liquid phase such as a Group IVB, VB or VIB metal, suitably tungsten, molybdenum, tantalum or niobium. The liquid phase or surface film provides fast transport through the electrode while the insoluble refractory metal provides a structural matrix for the electrode during operation. A trilayer structure that is stable and not subject to deadhesion comprises a first, thin layer of tungsten, an intermediate co-deposited layer of tungsten-platinum and a thin surface layer of platinum.

  9. Controlled in-situ dissolution of an alkali metal

    DOEpatents

    Jones, Jeffrey Donald; Dooley, Kirk John; Tolman, David Donald

    2012-09-11

    A method for the controllable dissolution of one or more alkali metals from a vessel containing a one or more alkali metals and/or one or more partially passivated alkali metals. The vessel preferably comprising a sodium, NaK or other alkali metal-cooled nuclear reactor that has been used. The alkali metal, preferably sodium, potassium or a combination thereof, in the vessel is exposed to a treatment liquid, preferably an acidic liquid, more preferably citric acid. Preferably, the treatment liquid is maintained in continuous motion relative to any surface of unreacted alkali metal with which the treatment liquid is in contact. The treatment liquid is preferably pumped into the vessel containing the one or more alkali metals and the resulting fluid is extracted and optionally further processed. Preferably, the resulting off-gases are processed by an off-gas treatment system and the resulting liquids are processed by a liquid disposal system. In one preferred embodiment, an inert gas is pumped into the vessel along with the treatment liquid.

  10. (abstract) Fundamental Mechanisms of Electrode Kinetics and Alkali Metal Atom Transport at the Alkali Beta'-Alumina/Porous Electrode/Alkali Metal Vapor Three Phase Boundary

    NASA Technical Reports Server (NTRS)

    Williams, R. M.; Jeffries-Nakamura, B.; Ryan, M. A.; Underwood, M. L.; O'Connor, D.; Kisor, A.; Kikkert, S. K.

    1993-01-01

    The mechanisms of electrode kinetics and mass transport of alkali metal oxidation and alkali metal cation reduction at the solid electrolyte/porous electrode boundary as well as alkali metal transport through porous metal electrodes has important applications in optimizing device performance in alkali metal thermal to electric converter (AMTEC) cells which are high temperature, high current density electrochemical cells. Basic studies of these processes also affords the opportunity to investigate a very basic electrochemical reaction over a wide range of conditions; and a variety of mass transport modes at high temperatures via electrochemical techniques. The temperature range of these investigations covers 700K to 1240K; the alkali metal vapor pressures range from about 10(sup -2) to 10(sup 2) Pa; and electrodes studied have included Mo, W, Mo/Na(sub 2)MoO(sub 4), W/Na(sub 2)WO(sub 4), WPt(sub x), and WRh(sub x) (1.0 < x < 6.0 ) with Na at Na-beta'-alumina, and Mo with K at K-beta'-alumina. Both liquid metal/solid electrolyte/alkali metal vapor and alkali metal vapor/solid electrolyte/vapor cells have been used to characterize the reaction and transport processes. We have previously reported evidence of ionic, free molecular flow, and surface transport of sodium in several types of AMTEC electrodes.

  11. Recent materials compatibility studies in refractory metal-alkali metal systems for space power applications.

    NASA Technical Reports Server (NTRS)

    Harrison, R. W.; Hoffman, E. E.; Davies, R. L.

    1972-01-01

    Advanced Rankine and other proposed space power systems utilize refractory metals in contact with both single-phase and two-phase alkali metals at elevated temperatures. A number of recent compatibility experiments are described which emphasize the excellent compatibility of refractory metals with the alkali metals, lithium, sodium, and potassium, under a variety of environmental conditions. The alkali metal compatibilities of tantalum-, columbium-, molybdenum-, and tungsten-base alloys are discussed.

  12. The 4843 Alkali Metal Storage Facility Closure Plan

    SciTech Connect

    Not Available

    1991-06-01

    The 4843 AMSF has been used primarily to provide a centralized building to receive and store dangerous and mixed alkali metal waste, including sodium and lithium, which has been generated at the Fast Flux Test Facility and at various other Hanford Site operations that used alkali metals. Most of the dangerous and mixed alkali metal waste received consists of retired equipment from liquid sodium processes. The unit continues to store material. In general, only solid alkali metal waste that is water reactive is stored at the 4843 AMSF. The 4843 AMSF will be closed in a manner consistent with Ecology guidelines and regulations (WAC 173-303-610). The general closure procedure is detailed as follows.

  13. Hall Determination of Atomic Radii of Alkali Metals

    ERIC Educational Resources Information Center

    Houari, Ahmed

    2008-01-01

    I will propose here an alternative method for determining atomic radii of alkali metals based on the Hall measurements of their free electron densities and the knowledge of their crystal structure. (Contains 2 figures.)

  14. Method for intercalating alkali metal ions into carbon electrodes

    DOEpatents

    Doeff, M.M.; Ma, Y.; Visco, S.J.; DeJonghe, L.

    1995-08-22

    A low cost, relatively flexible, carbon electrode for use in a secondary battery is described. A method is provided for producing same, including intercalating alkali metal salts such as sodium and lithium into carbon.

  15. Method for intercalating alkali metal ions into carbon electrodes

    DOEpatents

    Doeff, Marca M.; Ma, Yanping; Visco, Steven J.; DeJonghe, Lutgard

    1995-01-01

    A low cost, relatively flexible, carbon electrode for use in a secondary battery is described. A method is provided for producing same, including intercalating alkali metal salts such as sodium and lithium into carbon.

  16. Bioinorganic Chemistry of the Alkali Metal Ions.

    PubMed

    Kim, Youngsam; Nguyen, Thuy-Tien T; Churchill, David G

    2016-01-01

    The common Group 1 alkali metals are indeed ubiquitous on earth, in the oceans and in biological systems. In this introductory chapter, concepts involving aqueous chemistry and aspects of general coordination chemistry and oxygen atom donor chemistry are introduced. Also, there are nuclear isotopes of importance. A general discussion of Group 1 begins from the prevalence of the ions, and from a comparison of their ionic radii and ionization energies. While oxygen and water molecule binding have the most relevance to biology and in forming a detailed understanding between the elements, there is a wide range of basic chemistry that is potentially important, especially with respect to biological chelation and synthetic multi-dentate ligand design. The elements are widely distributed in life forms, in the terrestrial environment and in the oceans. The details about the workings in animal, as well as plant life are presented in this volume. Important biometallic aspects of human health and medicine are introduced as well. Seeing as the elements are widely present in biology, various particular endogenous molecules and enzymatic systems can be studied. Sodium and potassium are by far the most important and central elements for consideration. Aspects of lithium, rubidium, cesium and francium chemistry are also included; they help in making important comparisons related to the coordination chemistry of Na(+) and K(+). Physical methods are also introduced. PMID:26860297

  17. Ternary alkali-metal and transition metal or metalloid acetylides as alkali-metal intercalation electrodes for batteries

    DOEpatents

    Nemeth, Karoly; Srajer, George; Harkay, Katherine C; Terdik, Joseph Z

    2015-02-10

    Novel intercalation electrode materials including ternary acetylides of chemical formula: A.sub.nMC.sub.2 where A is alkali or alkaline-earth element; M is transition metal or metalloid element; C.sub.2 is reference to the acetylide ion; n is an integer that is 0, 1, 2, 3 or 4 when A is alkali element and 0, 1, or 2 when A is alkaline-earth element. The alkali elements are Lithium (Li), Sodium (Na), Potassium (K), Rubidium (Rb), Cesium (Cs) and Francium (Fr). The alkaline-earth elements are Berilium (Be), Magnesium (Mg), Calcium (Ca), Strontium (Sr), Barium (Ba), and Radium (Ra). M is a transition metal that is any element in groups 3 through 12 inclusive on the Periodic Table of Elements (elements 21 (Sc) to element 30 (Zn)). In another exemplary embodiment, M is a metalloid element.

  18. Rock Degradation by Alkali Metals: A Possible Lunar Erosion Mechanism.

    PubMed

    Naughton, J J; Barnes, I L; Hammond, D A

    1965-08-01

    When rocks melt under ultrahigh-vacuum conditions, their alkali components volatilize as metals. These metal vapors act to comminute polycrystalline rocks to their component minerals. The resultant powder is porous and loosely packed and its characteristics may be compatible with the lunar surface as revealed by the Ranger photographs. If meteorite impact or lunar volcanism has produced vaporization or areas of molten lava, alkali erosion may have given dust of this character in adjacent solid areas. PMID:17747570

  19. Electrochemical cell having an alkali-metal-nitrate electrode

    DOEpatents

    Roche, M.F.; Preto, S.K.

    1982-06-04

    A power-producing secondary electrochemical cell includes a molten alkali metal as the negative-electrode material and a molten-nitrate salt as the positive-electrode material. The molten material in the respective electrodes are separated by a solid barrier of alkali-metal-ion conducting material. A typical cell includes active materials of molten sodium separated from molten sodium nitrate and other nitrates in mixture by a layer of sodium ..beta..'' alumina.

  20. Theory of Magnetotransport Anomalies in Alkali Metals

    NASA Astrophysics Data System (ADS)

    Zhu, Xiaodong

    The galvanomagnetic properties of alkali metals, especially those of potassium, are studied taking into account the existence of an incommensurate change-density wave (CDW) structure. Occurrence of the CDW broken symmetry truncates the Fermi surface with a large number of energy gaps. Furthermore, any macroscopic crystal is likely divided into CDW (')Q-domains. An orientational (')Q-texture leads to a preferred direction in the crystal. For such an exotic system the effective magnetoresistivity tensor is anomalous and is derived for various magnetic fields. The residual (zero-field) resistance is also anisotropic. For fields 0.5 - 3T, Hall coefficients are found to be anisotropic, and a longitudinal-transverse mixing effect is discovered. The diagonal elements of the magnetoresistivity tensor are found to have a linear magnetoresistance. When the field is increased above 4T sharp open-orbit magnetoresistance spectrum develops. From the theoretical magnetoresistivity tensor, the induced-torque amplitude and phase patterns for potassium spheres are calculated. The theory quantitatively explains all of the induced-torque anomalies found experimentally in the last fourteen years. An interacting electron system, which is free of the CDW instabilities, is also studied by considering its spin response to a weak sinusoidal magnetic field. The many-body correction G(,-)((')q,(omega)) caused by exchange and correlation is introduced to describe the correct wave -vector- and frequency-dependent spin susceptibility. The exact behavior of G(,-)((')q,(omega)) in the large-q limit is shown to be related to the pair distribution function g((')r) at r = 0. G(,-)((')q,(omega)) (--->) 4g(0)-1 /3, as q (--->) (INFIN).At metallic densities this value is negative, opposite in sign to the limit at small wave vectors. Thus the spin susceptibility for large wave vectors is suppressed, rather than enhanced, by many-body effects.

  1. Two-phase alkali-metal experiments in reduced gravity

    SciTech Connect

    Antoniak, Z.I.

    1986-06-01

    Future space missions envision the use of large nuclear reactors utilizing either a single or a two-phase alkali-metal working fluid. The design and analysis of such reactors require state-of-the-art computer codes that can properly treat alkali-metal flow and heat transfer in a reduced-gravity environment. A literature search of relevant experiments in reduced gravity is reported on here, and reveals a paucity of data for such correlations. The few ongoing experiments in reduced gravity are noted. General plans are put forth for the reduced-gravity experiments which will have to be performed, at NASA facilities, with benign fluids. A similar situation exists regarding two-phase alkali-metal flow and heat transfer, even in normal gravity. Existing data are conflicting and indequate for the task of modeling a space reactor using a two-phase alkali-metal coolant. The major features of past experiments are described here. Data from the reduced-gravity experiments with innocuous fluids are to be combined with normal gravity data from the two-phase alkali-metal experiments. Analyses undertaken here give every expectation that the correlations developed from this data base will provide a valid representation of alkali-metal heat transfer and pressure drop in reduced gravity.

  2. Alkali metal yttrium neo-pentoxide double alkoxide precursors to alkali metal yttrium oxide nanomaterials

    DOE PAGESBeta

    Boyle, Timothy J.; Neville, Michael L.; Sears, Jeremiah Matthew; Cramer, Roger

    2016-03-15

    In this study, a series of alkali metal yttrium neo-pentoxide ([AY(ONep)4]) compounds were developed as precursors to alkali yttrium oxide (AYO2) nanomaterials. The reaction of yttrium amide ([Y(NR2)3] where R=Si(CH3)3) with four equivalents of H-ONep followed by addition of [A(NR2)] (A=Li, Na, K) or Ao (Ao=Rb, Cs) led to the formation of a complex series of AnY(ONep)3+n species, crystallographically identified as [Y2Li3(μ3-ONep)(μ3-HONep)(μ-ONep)5(ONep)3(HONep)2] (1), [YNa2(μ3-ONep)4(ONep)]2 (2), {[Y2K3(μ3-ONep)3(μ-ONep)4(ONep)2(ηξ-tol)2][Y4K2(μ4-O)(μ3-ONep)8(ONep)4]•ηx-tol]} (3), [Y4K2(μ4-O)(μ3-ONep)8(ONep)4] (3a), [Y2Rb3(μ4-ONep)3(μ-ONep)6] (4), and [Y2Cs4(μ6-O)(μ3-ONep)6(μ3-HONep)2(ONep)2(ηx-tol)4]•tol (5). Compounds 1–5 were investigated as single source precursors to AYOx nanomaterials following solvothermal routes (pyridine, 185 °C for 24h). The final products after thermal processing weremore » found by powder X-ray diffraction experiments to be Y2O3 with variable sized particles based on transmission electron diffraction. Energy dispersive X-ray spectroscopy studies indicated that the heavier alkali metal species were present in the isolated nanomaterials.« less

  3. Tin-containing silicates: alkali salts improve methyl lactate yield from sugars.

    PubMed

    Tolborg, Søren; Sádaba, Irantzu; Osmundsen, Christian M; Fristrup, Peter; Holm, Martin S; Taarning, Esben

    2015-02-01

    This study focuses on increasing the selectivity to methyl lactate from sugars using stannosilicates as heterogeneous catalyst. All group I ions are found to have a promoting effect on the resulting methyl lactate yield. Besides, the alkali ions can be added both during the preparation of the catalyst or directly to the solvent mixture to achieve the highest reported yield of methyl lactate (ca. 75 %) from sucrose at 170 °C in methanol. The beneficial effect of adding alkali to the reaction media applies not only to highly defect-free Sn-Beta prepared through the fluoride route, but also to materials prepared by post-treatment of dealuminated commercial Beta zeolites, as well as ordered mesoporous stannosilicates, in this case Sn-MCM-41 and Sn-SBA-15. These findings open the door to the possibility of using other preparation methods or different Sn-containing silicates with equally high methyl lactate yields as Sn-Beta. PMID:25605624

  4. Cellular morphology of organic-inorganic hybrid foams based on alkali alumino-silicate matrix

    SciTech Connect

    Verdolotti, Letizia; Capasso, Ilaria; Lavorgna, Marino; Liguori, Barbara; Caputo, Domenico; Iannace, Salvatore

    2014-05-15

    Organic-inorganic hybrid foams based on an alkali alumino-silicate matrix were prepared by using different foaming methods. Initially, the synthesis of an inorganic matrix by using aluminosilicate particles, activated through a sodium silicate solution, was performed at room temperature. Subsequently the viscous paste was foamed by using three different methods. In the first method, gaseous hydrogen produced by the oxidization of Si powder in an alkaline media, was used as blowing agent to generate gas bubbles in the paste. In the second method, the porous structure was generated by mixing the paste with a “meringue” type of foam previously prepared by whipping, under vigorous stirring, a water solution containing vegetal proteins as surfactants. In the third method, a combination of these two methods was employed. The foamed systems were consolidated for 24 hours at 40°C and then characterized by FTIR, X-Ray diffraction, scanning electron microscopy (SEM) and compression tests. Low density foams (∼500 Kg/m{sup 3}) with good cellular structure and mechanical properties were obtained by combining the “meringue” approach with the use of the chemical blowing agent based on Si.

  5. Compliant alkali silicate sealing glass for solid oxide fuel cell applications: the effect of protective alumina coating on electrical stability in dual environment

    SciTech Connect

    Chou, Y. S.; Choi, Jung-Pyung; Stevenson, Jeffry W.

    2012-12-01

    An alkali-containing silicate glass was recently proposed as a potential sealant for solid oxide fuel cells (SOFC). The glass contains appreciable amount of alkalis and retains its glassy microstructure at elevated temperatures over time. It is more compliant as compared to conventional glass-ceramics sealants and could potentially heal cracks during thermal cycling. In previous papers the thermal cycle stability, thermal stability and chemical compatibility were reported with yttria-stabilized zirconia (YSZ) electrolyte and YSZ-coated ferritic stainless steel interconnect. In this paper, we report the electrical stability of the compliant glass with aluminized AISI441 interconnect material under DC load in dual environment at 700-800oC. Apparent electrical resistivity was measured with a 4-point method for the glass sealed between two aluminized AISI441 metal coupons as well as plain AISI441 substrates. The results showed good electrical stability with the aluminized AISI441 substrate, while unstable behavior was observed for un-coated substrates. In addition, interfacial microstructure was examined with scanning electron microscopy and correlated with the measured resistivity results. Overall, the alumina coating demonstrated good chemical stability with the alkali-containing silicate sealing glass under DC loading.

  6. On-chip fabrication of alkali-metal vapor cells utilizing an alkali-metal source tablet

    NASA Astrophysics Data System (ADS)

    Tsujimoto, K.; Ban, K.; Hirai, Y.; Sugano, K.; Tsuchiya, T.; Mizutani, N.; Tabata, O.

    2013-11-01

    We describe a novel on-chip microfabrication technique for the alkali-metal vapor cell of an optically pumped atomic magnetometer (OPAM), utilizing an alkali-metal source tablet (AMST). The newly proposed AMST is a millimeter-sized piece of porous alumina whose considerable surface area holds deposited alkali-metal chloride (KCl) and barium azide (BaN6), source materials that effectively produce alkali-metal vapor at less than 400 °C. Our experiments indicated that the most effective pore size of the AMST is between 60 and 170 µm. The thickness of an insulating glass spacer holding the AMST was designed to confine generated alkali metal to the interior of the vapor cell during its production, and an integrated silicon heater was designed to seal the device using a glass frit, melted at an optimum temperature range of 460-490 °C that was determined by finite element method thermal simulation. The proposed design and AMST were used to successfully fabricate a K cell that was then operated as an OPAM with a measured sensitivity of 50 pT. These results demonstrate that the proposed concept for on-chip microfabrication of alkali-metal vapor cells may lead to effective replacement of conventional glassworking approaches.

  7. Upgrading of petroleum oil feedstocks using alkali metals and hydrocarbons

    SciTech Connect

    Gordon, John Howard

    2014-09-09

    A method of upgrading an oil feedstock by removing heteroatoms and/or one or more heavy metals from the oil feedstock composition. This method reacts the oil feedstock with an alkali metal and an upgradant hydrocarbon. The alkali metal reacts with a portion of the heteroatoms and/or one or more heavy metals to form an inorganic phase separable from the organic oil feedstock material. The upgradant hydrocarbon bonds to the oil feedstock material and increases the number of carbon atoms in the product. This increase in the number of carbon atoms of the product increases the energy value of the resulting oil feedstock.

  8. Alkali metal adsorption on Al(111)

    NASA Astrophysics Data System (ADS)

    Andersen, J. N.; Lundgren, E.; Nyholm, R.; Qvarford, M.

    1993-06-01

    The submonolayer adsorption of Na, K, Rb, and Cs on the Al(111) surface at 100 K and at room temperature is investigated by high resolution core level spectroscopy and low energy electron diffraction. It is found that the first alkali atoms on the surface adsorb at surface defects. At higher coverages, up to approximately one third of the maximum submonolayer coverage, alkali atoms adsorbed at defects coexist with a dispersed phase. At higher coverages island formation is found to occur for the majority of the systems. It is argued that all of the ordered structures formed at room temperature involve a disruption of the Al(111) surface in contrast to the situation at 100 K where the alkali atoms adsorb as adatoms.

  9. Intrinsic differences in atomic ordering of calcium (alumino)silicate hydrates in conventional and alkali-activated cements

    SciTech Connect

    White, Claire E.; Daemen, Luke L.; Hartl, Monika; Page, Katharine

    2015-01-15

    The atomic structures of calcium silicate hydrate (C–S–H) and calcium (–sodium) aluminosilicate hydrate (C–(N)–A–S–H) gels, and their presence in conventional and blended cement systems, have been the topic of significant debate over recent decades. Previous investigations have revealed that synthetic C–S–H gel is nanocrystalline and due to the chemical similarities between ordinary Portland cement (OPC)-based systems and low-CO{sub 2} alkali-activated slags, researchers have inferred that the atomic ordering in alkali-activated slag is the same as in OPC–slag cements. Here, X-ray total scattering is used to determine the local bonding environment and nanostructure of C(–A)–S–H gels present in hydrated tricalcium silicate (C{sub 3}S), blended C{sub 3}S–slag and alkali-activated slag, revealing the large intrinsic differences in the extent of nanoscale ordering between C–S–H derived from C{sub 3}S and alkali-activated slag systems, which may have a significant influence on thermodynamic stability, and material properties at higher length scales, including long term durability of alkali-activated cements.

  10. Characterization of chitin-metal silicates as binding superdisintegrants.

    PubMed

    Rashid, Iyad; Daraghmeh, Nidal; Al-Remawi, Mayyas; Leharne, Stephen A; Chowdhry, Babur Z; Badwan, Adnan

    2009-12-01

    When chitin is used in pharmaceutical formulations, processing of chitin with metal silicates is advantageous, from both an industrial and pharmaceutical perspective, compared to processing using silicon dioxide. Unlike the use of acidic and basic reagents for the industrial preparation of chitin-silica particles, coprecipitation of metal silicates is dependent upon a simple replacement reaction between sodium silicate and metal chlorides. When coprecipitated onto chitin particles, aluminum, magnesium, or calcium silicates result in nonhygroscopic, highly compactable/disintegrable compacts. Disintegration and hardness parameters for coprocessed chitin compacts were investigated and found to be independent of the particle size. Capillary action appears to be the major contributor to both water uptake and the driving force for disintegration of compacts. The good compaction and compression properties shown by the chitin-metal silicates were found to be strongly dependent upon the type of metal silicate coprecipitated onto chitin. In addition, the inherent binding and disintegration abilities of chitin-metal silicates are useful in pharmaceutical applications when poorly compressible and/or highly nonpolar drugs need to be formulated. PMID:19691098

  11. Elucidation of transport mechanism and enhanced alkali ion transference numbers in mixed alkali metal-organic ionic molten salts.

    PubMed

    Chen, Fangfang; Forsyth, Maria

    2016-07-28

    Mixed salts of Ionic Liquids (ILs) and alkali metal salts, developed as electrolytes for lithium and sodium batteries, have shown a remarkable ability to facilitate high rate capability for lithium and sodium electrochemical cycling. It has been suggested that this may be due to a high alkali metal ion transference number at concentrations approaching 50 mol% Li(+) or Na(+), relative to lower concentrations. Computational investigations for two IL systems illustrate the formation of extended alkali-anion aggregates as the alkali metal ion concentration increases. This tends to favor the diffusion of alkali metal ions compared with other ionic species in electrolyte solutions; behavior that has recently been reported for Li(+) in a phosphonium ionic liquid, thus an increasing alkali transference number. The mechanism of alkali metal ion diffusion via this extended coordination environment present at high concentrations is explained and compared to the dynamics at lower concentrations. Heterogeneous alkali metal ion dynamics are also evident and, somewhat counter-intuitively, it appears that the faster ions are those that are generally found clustered with the anions. Furthermore these fast alkali metal ions appear to correlate with fastest ionic liquid solvent ions. PMID:27375042

  12. Neuropsychiatric manifestations of alkali metal deficiency and excess.

    PubMed

    Yung, C Y

    1984-01-01

    The alkali metals from the Group IA of the periodic table (lithium, sodium, potassium, rubidium, cesium and francium) are reviewed. The neuropsychiatric aspects of alkali metal deficiencies and excesses (intoxications) are described. Emphasis was placed on lithium due to its clinical uses. The signs and symptoms of these conditions are characterized by features of an organic brain syndrome with delirium and encephalopathy prevailing. There are no clinically distinctive features that could be reliably used for diagnoses. Sodium and potassium are two essential alkali metals in man. Lithium is used as therapeutic agent in bipolar affective disorders. Rubidium has been investigated for its antidepressant effect in a group of psychiatric disorders. Cesium is under laboratory investigation for its role in carcinogenesis and in depressive illness. Very little is known of francium due to its great instability for experimental study. PMID:6395136

  13. Neuropsychiatric manifestations of alkali metal deficiency and excess

    SciTech Connect

    Yung, C.Y.

    1984-01-01

    The alkali metals from the Group IA of the periodic table (lithium, sodium, potassium, rubidium, cesium and francium) are reviewed. The neuropsychiatric aspects of alkali metal deficiencies and excesses (intoxications) are described. Emphasis was placed on lithium due to its clinical uses. The signs and symptoms of these conditions are characterized by features of an organic brain syndrome with delirium and encephalopathy prevailing. There are no clinically distinctive features that could be reliably used for diagnoses. Sodium and potassium are two essential alkali metals in man. Lithium is used as therapeutic agent in bipolar affective disorders. Rubidium has been investigated for its antidepressant effect in a group of psychiatric disorders. Cesium is under laboratory investigation for its role in carcinogenesis and in depressive illness. Very little is known of francium due to its great instability for experimental study.

  14. Superconductivity above 30 K in alkali-metal-doped hydrocarbon

    PubMed Central

    Xue, Mianqi; Cao, Tingbing; Wang, Duming; Wu, Yue; Yang, Huaixin; Dong, Xiaoli; He, Junbao; Li, Fengwang; Chen, G. F.

    2012-01-01

    The recent discovery of superconductivity with a transition temperature (Tc) at 18 K in Kxpicene has extended the possibility of high-Tc superconductors in organic materials. Previous experience based on similar hydrocarbons, like alkali-metal doped phenanthrene, suggested that even higher transition temperatures might be achieved in alkali-metals or alkali-earth-metals doped such polycyclic-aromatic-hydrocarbons (PAHs), a large family of molecules composed of fused benzene rings. Here we report the discovery of high-Tc superconductivity at 33 K in K-doped 1,2:8,9-dibenzopentacene (C30H18). To our best knowledge, it is higher than any Tc reported previously for an organic superconductor under ambient pressure. This finding provides an indication that superconductivity at much higher temperature may be possible in such PAHs system and is worthy of further exploration. PMID:22548129

  15. Spill-Resistant Alkali-Metal-Vapor Dispenser

    NASA Technical Reports Server (NTRS)

    Klipstein, William

    2005-01-01

    A spill-resistant vessel has been developed for dispensing an alkali-metal vapor. Vapors of alkali metals (most commonly, cesium or rubidium, both of which melt at temperatures slightly above room temperature) are needed for atomic frequency standards, experiments in spectroscopy, and experiments in laser cooling. Although the present spill-resistant alkali-metal dispenser was originally intended for use in the low-gravity environment of outer space, it can also be used in normal Earth gravitation: indeed, its utility as a vapor source was confirmed by use of cesium in a ground apparatus. The vessel is made of copper. It consists of an assembly of cylinders and flanges, shown in the figure. The uppermost cylinder is a fill tube. Initially, the vessel is evacuated, the alkali metal charge is distilled into the bottom of the vessel, and then the fill tube is pinched closed to form a vacuum seal. The innermost cylinder serves as the outlet for the vapor, yet prevents spilling by protruding above the surface of the alkali metal, no matter which way or how far the vessel is tilted. In the event (unlikely in normal Earth gravitation) that any drops of molten alkali metal have been shaken loose by vibration and are floating freely, a mesh cap on top of the inner cylinder prevents the drops from drifting out with the vapor. Liquid containment of the equivalent of 1.2 grams of cesium was confirmed for all orientations with rubbing alcohol in one of the prototypes later used with cesium.

  16. Transport properties of alkali metal doped fullerides

    SciTech Connect

    Yadav, Daluram Yadav, Nishchhal

    2015-07-31

    We have studied the intercage interactions between the adjacent C{sub 60} cages and expansion of lattice due to the intercalation of alkali atoms based on the spring model to estimate phonon frequencies from the dynamical matrix for the intermolecular alkali-C{sub 60} phonons. We considered a two-peak model for the phonon density of states to investigate the nature of electron pairing mechanism for superconducting state in fullerides. Coulomb repulsive parameter and the electron phonon coupling strength are obtained within the random phase approximation. Transition temperature, T{sub c}, is obtained in a situation when the free electrons in lowest molecular orbital are coupled with alkali-C{sub 60} phonons as 5 K, which is much lower as compared to reported T{sub c} (20 K). The superconducting pairing is mainly driven by the high frequency intramolecular phonons and their effects enhance it to 22 K. The importance of the present study, the pressure effect and normal state transport properties are calculated within the same model leading superconductivity.

  17. Transport properties of alkali metal doped fullerides

    NASA Astrophysics Data System (ADS)

    Yadav, Daluram; Yadav, Nishchhal

    2015-07-01

    We have studied the intercage interactions between the adjacent C60 cages and expansion of lattice due to the intercalation of alkali atoms based on the spring model to estimate phonon frequencies from the dynamical matrix for the intermolecular alkali-C60 phonons. We considered a two-peak model for the phonon density of states to investigate the nature of electron pairing mechanism for superconducting state in fullerides. Coulomb repulsive parameter and the electron phonon coupling strength are obtained within the random phase approximation. Transition temperature, Tc, is obtained in a situation when the free electrons in lowest molecular orbital are coupled with alkali-C60 phonons as 5 K, which is much lower as compared to reported Tc (20 K). The superconducting pairing is mainly driven by the high frequency intramolecular phonons and their effects enhance it to 22 K. The importance of the present study, the pressure effect and normal state transport properties are calculated within the same model leading superconductivity.

  18. Interaction of alkali-metal overlayers with oxygen

    SciTech Connect

    Hrbek, J.; Xu, G.; Sham, T.K.; Shek, M.L.

    1989-05-01

    The interaction of oxygen with alkali metals (Li, Na, K, and Cs) was studied with valence and core-level photoemission (PE) using synchrotron radiation and by multiple mass thermal desorption (TDS). During a stepwise coadsorption of oxygen at 80 K, an increase in the emission intensity, a linewidth broadening, and a negative binding-energy shift of alkali-metal core levels is observed. Two stages of oxygen adsorption are identified in PE and TDS. In the low O/sub 2/ exposure range, an oxide species is formed; at higher exposures, peroxide and superoxide species are observed in Na, K, and Cs. The potassium--oxygen interaction is discussed in detail.

  19. Alkali Silicate Glass Coatings for Mitigating the Risks of Tin Whiskers

    NASA Astrophysics Data System (ADS)

    Hillman, Dave; Wilcoxon, Ross; Lower, Nate; Grossman, Dan

    2015-12-01

    Alkali silicate glass (ASG) coatings were investigated as a possible method for inhibiting tin whisker initiation and growth. The aqueous-based ASG formulations used in this study were deposited with equipment and conditions that are typical of those used to apply conventional conformal coatings. Processes for controlling ASG coating properties were developed, and a number of ASG-based coating combinations were applied to test components with pure tin surfaces. Coatings were applied both in a laboratory environment at Rockwell Collins and in a manufacturing environment at Plasma Ruggedized Solutions. Testing in elevated humidity/temperature environments and subsequent inspection of the test articles identified coating combinations that inhibited tin whisker growth as well as other material combinations that actually accelerated tin whisker growth. None of the coatings evaluated in this study, including conventional acrylic and Parylene conformal coatings, completely prevented the formation of tin whiskers. Two of the coatings were particularly effective at reducing the risks of whisker growth, albeit through different mechanisms. Parylene conformal coating almost, but not completely, eliminated whisker formation, and only a few tin whiskers were found on these surfaces during the study. A composite of ASG and alumina nanoparticles inhibited whisker formation to a lesser degree than Parylene, but did disrupt whisker growth mechanisms so as to inhibit the formation of long, and more dangerous, tin whiskers. Additional testing also demonstrated that the conformal coatings had relatively little effect on the dielectric loss of a stripline test structure operating at frequencies over 30 GHz.

  20. Maternal exposure to alkali, alkali earth, transition and other metals: Concentrations and predictors of exposure.

    PubMed

    Hinwood, A L; Stasinska, A; Callan, A C; Heyworth, J; Ramalingam, M; Boyce, M; McCafferty, P; Odland, J Ø

    2015-09-01

    Most studies of metals exposure focus on the heavy metals. There are many other metals (the transition, alkali and alkaline earth metals in particular) in common use in electronics, defense industries, emitted via combustion and which are naturally present in the environment, that have received limited attention in terms of human exposure. We analysed samples of whole blood (172), urine (173) and drinking water (172) for antimony, beryllium, bismuth, cesium, gallium, rubidium, silver, strontium, thallium, thorium and vanadium using ICPMS. In general most metals concentrations were low and below the analytical limit of detection with some high concentrations observed. Few factors examined in regression models were shown to influence biological metals concentrations and explained little of the variation. Further study is required to establish the source of metals exposures at the high end of the ranges of concentrations measured and the potential for any adverse health impacts in children. PMID:25984984

  1. Solid state cell with alkali metal halo-alkali thiocyanate electrolyte

    SciTech Connect

    Rao, B. M.; Silbernagel, B. G.

    1980-02-26

    A novel electrochemical cell is disclosed utilizing: (A) an anode which contains an alkali metal as an anode-active material; (B) a cathode and (C) an electrolyte comprising an electrolytically effective amount of one or more compounds having the formula: (Ax)ma'scn wherein a is an alkali metal, X is a halogen, a' is an alkali metal and 0.1 < or = N < or = 10. Preferred systems include lithium-containing anodes, lithium-containing electrolytes and cathodes which contain cathode-active material selected from the group consisting of cathode-active sulfurs, halogens, halides, chromates, phosphates, oxides and chalcogenides, especially those chalcogenides of the empirical formula mzm wherein M is one or more metals selected from the group consisting of iron, titanium, zirconium, hafnium, niobium, tantalum and vanadium, Z is one or more chalcogens selected from the group consisting of oxygen, sulfur, selenium and tellurium, and M is a numerical value between about 1.8 and about 3.2.

  2. Compliant alkali silicate sealing glass for solid oxide fuel cell applications: the effect of protective YSZ coating on electrical stability in dual environment

    SciTech Connect

    Chou, Y. S.; Thomsen, Edwin C.; Choi, Jung-Pyung; Stevenson, Jeffry W.

    2012-03-15

    Recently, compliant sealing glass has been proposed as a potential candidate sealant for solid oxide fuel cell (SOFC) applications. In a previous paper, the thermal stability and chemical compatibility were reported for a compliant alkali-containing silicate glass sealed between anode supported YSZ bi-layer and YSZ-coated stainless steel interconnect. In this paper, we will report the electrical stability of the compliant glass under a DC load and dual environment at 700-800 degrees C. Apparent electrical resistivity was measured with a 4-point method for the glass sealed between two plain SS441 metal coupons or YSZ-coated aluminized substrates. The results showed instability with plain SS441 at 800 degrees C, but stable behavior of increasing resistivity with time was observed with the YSZ coated SS441. In addition, results of interfacial microstructure analysis with scanning electron microscopy will be correlated with the measured resistivity results. Overall, the YSZ coating demonstrated chemically stability with the alkali-containing compliant silicate sealing glass under electrical field and dual environments.

  3. Structural models for alkali-metal complexes of polyacetylene

    NASA Astrophysics Data System (ADS)

    Murthy, N. S.; Shacklette, L. W.; Baughman, R. H.

    1990-02-01

    Structural models for a stage-2 complex are proposed for polyacetylene doped with less than about 0.1 potassium or rubidium atoms per carbon. These structures utilize as a basic motif an alkali-metal column surrounded by four planar-zig-zag polyacetylene chains, a structure found at the highest dopant levels. In the new stage-2 structures, each polyacetylene chain neighbors only one alkali-metal column, so the phase contains four polymer chains per alkali-metal column. Basic structural aspects for stage-1 and stage-2 structures are now established for both potassium- and rubidium-doped polyacetylene. X-ray-diffraction and electrochemical data show that undoped and doped phases coexist at low dopant concentrations (<0.06 K atom per C). X-ray-diffraction data, down to a Bragg spacing of 1.3 Å, for polyacetylene heavily doped with potassium (0.125-0.167 K atom per C) is fully consistent with our previously proposed stage-1 tetragonal unit cell containing two polyacetylene chains per alkali-metal column. There is no evidence for our samples requiring a distortion to a monoclinic unit cell as reported by others for heavily doped samples. The nature of structural transformations and the relationship between structure and electronic properties are discussed for potassium-doped polyacetylene.

  4. Method of assembling and sealing an alkali metal battery

    DOEpatents

    Elkins, P.E.; Bell, J.E.; Harlow, R.A.; Chase, G.G.

    1983-03-01

    A method of initially assembling and then subsequently hermetically sealing a container portion of an alkali metal battery to a ceramic portion of such a battery is disclosed. Sealing surfaces are formed respectively on a container portion and a ceramic portion of an alkali metal battery. These sealing surfaces are brought into juxtaposition and a material is interposed there between. This interposed material is one which will diffuse into sealing relationship with both the container portion and the ceramic portion of the alkali metal battery at operational temperatures of such a battery. A pressure is applied between these sealing surfaces to cause the interposed material to be brought into intimate physical contact with such juxtaposed surfaces. A temporary sealing material which will provide a seal against a flow of alkali metal battery reactants there through at room temperatures and is applied over the juxtaposed sealing surfaces and material interposed there between. The entire assembly is heated to an operational temperature so that the interposed material diffuses into the container portion and the ceramic portion to form a hermetic seal there between. The pressure applied to the juxtaposed sealing surfaces is maintained in order to ensure the continuation of the hermetic seal. 4 figs.

  5. High capacity nickel battery material doped with alkali metal cations

    DOEpatents

    Jackovitz, John F.; Pantier, Earl A.

    1982-05-18

    A high capacity battery material is made, consisting essentially of hydrated Ni(II) hydroxide, and about 5 wt. % to about 40 wt. % of Ni(IV) hydrated oxide interlayer doped with alkali metal cations selected from potassium, sodium and lithium cations.

  6. Method of assembling and sealing an alkali metal battery

    DOEpatents

    Elkins, Perry E.; Bell, Jerry E.; Harlow, Richard A.; Chase, Gordon G.

    1983-01-01

    A method of initially assembling and then subsequently hermetically sealing a container portion of an alkali metal battery to a ceramic portion of such a battery is disclosed. Sealing surfaces are formed respectively on a container portion and a ceramic portion of an alkali metal battery. These sealing surfaces are brought into juxtaposition and a material is interposed therebetween. This interposed material is one which will diffuse into sealing relationship with both the container portion and the ceramic portion of the alkali metal battery at operational temperatures of such a battery. A pressure is applied between these sealing surfaces to cause the interposed material to be brought into intimate physical contact with such juxtaposed surfaces. A temporary sealing material which will provide a seal against a flow of alkali metal battery reactants therethrough at room temperatures and is applied over the juxtaposed sealing surfaces and material interposed therebetween. The entire assembly is heated to an operational temperature so that the interposed material diffuses into the container portion and the ceramic portion to form a hermetic seal therebetween. The pressure applied to the juxtaposed sealing surfaces is maintained in order to ensure the continuation of the hermetic seal.

  7. Aqueous alkali metal hydroxide insoluble cellulose ether membrane

    NASA Technical Reports Server (NTRS)

    Hoyt, H. E.; Pfluger, H. L. (Inventor)

    1969-01-01

    A membrane that is insoluble in an aqueous alkali metal hydroxide medium is described. The membrane is a resin which is a water-soluble C2-C4 hydroxyalkyl cellulose ether polymer and an insolubilizing agent for controlled water sorption, a dialytic and electrodialytic membrane. It is particularly useful as a separator between electrodes or plates in an alkaline storage battery.

  8. 40 CFR 721.5452 - Alkali metal salt of halogenated organoborate (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkali metal salt of halogenated... Specific Chemical Substances § 721.5452 Alkali metal salt of halogenated organoborate (generic). (a... generically as alkali metal salt of halogenated organoborate (PMN P-00-0638) is subject to reporting...

  9. 40 CFR 721.5985 - Fatty alkyl phosphate, alkali metal salt (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Fatty alkyl phosphate, alkali metal... Specific Chemical Substances § 721.5985 Fatty alkyl phosphate, alkali metal salt (generic). (a) Chemical... as a fatty alkyl phosphate, alkali metal salt (PMN P-99-0385) is subject to reporting under...

  10. 40 CFR 721.5452 - Alkali metal salt of halogenated organoborate (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkali metal salt of halogenated... Specific Chemical Substances § 721.5452 Alkali metal salt of halogenated organoborate (generic). (a... generically as alkali metal salt of halogenated organoborate (PMN P-00-0638) is subject to reporting...

  11. 40 CFR 721.5452 - Alkali metal salt of halogenated organoborate (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkali metal salt of halogenated... Specific Chemical Substances § 721.5452 Alkali metal salt of halogenated organoborate (generic). (a... generically as alkali metal salt of halogenated organoborate (PMN P-00-0638) is subject to reporting...

  12. 40 CFR 721.5452 - Alkali metal salt of halogenated organoborate (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkali metal salt of halogenated... Specific Chemical Substances § 721.5452 Alkali metal salt of halogenated organoborate (generic). (a... generically as alkali metal salt of halogenated organoborate (PMN P-00-0638) is subject to reporting...

  13. High Pressure/Temperature Metal Silicate Partitioning of Tungsten

    NASA Technical Reports Server (NTRS)

    Shofner, G. A.; Danielson, L.; Righter, K.; Campbell, A. J.

    2010-01-01

    The behavior of chemical elements during metal/silicate segregation and their resulting distribution in Earth's mantle and core provide insight into core formation processes. Experimental determination of partition coefficients allows calculations of element distributions that can be compared to accepted values of element abundances in the silicate (mantle) and metallic (core) portions of the Earth. Tungsten (W) is a moderately siderophile element and thus preferentially partitions into metal versus silicate under many planetary conditions. The partitioning behavior has been shown to vary with temperature, silicate composition, oxygen fugacity, and pressure. Most of the previous work on W partitioning has been conducted at 1-bar conditions or at relatively low pressures, i.e. <10 GPa, and in two cases at or near 20 GPa. According to those data, the stronger influences on the distribution coefficient of W are temperature, composition, and oxygen fugacity with a relatively slight influence in pressure. Predictions based on extrapolation of existing data and parameterizations suggest an increased pressured dependence on metal/ silicate partitioning of W at higher pressures 5. However, the dependence on pressure is not as well constrained as T, fO2, and silicate composition. This poses a problem because proposed equilibration pressures for core formation range from 27 to 50 GPa, falling well outside the experimental range, therefore requiring exptrapolation of a parametereized model. Higher pressure data are needed to improve our understanding of W partitioning at these more extreme conditions.

  14. Thermodynamics of Liquid Alkali Metals and Their Binary Alloys

    NASA Astrophysics Data System (ADS)

    Thakor, P. B.; Patel, Minal H.; Gajjar, P. N.; Jani, A. R.

    2009-07-01

    The theoretical investigation of thermodynamic properties like internal energy, entropy, Helmholtz free energy, heat of mixing (ΔE) and entropy of mixing (ΔS) of liquid alkali metals and their binary alloys are reported in the present paper. The effect of concentration on the thermodynamic properties of Ac1Bc2 alloy of the alkali-alkali elements is investigated and reported for the first time using our well established local pseudopotential. To investigate influence of exchange and correlation effects, we have used five different local field correction functions viz; Hartree(H), Taylor(T), Ichimaru and Utsumi(IU), Farid et al. (F) and Sarkar et al. (S). The increase of concentration C2, increases the internal energy and Helmholtz free energy of liquid alloy Ac1Bc2. The behavior of present computation is not showing any abnormality in the outcome and hence confirms the applicability of our model potential in explaining the thermodynamics of liquid binary alloys.

  15. Release and sorption of alkali metals in coal conversion

    SciTech Connect

    Witthohn, A.; Oeltjen, L.; Hilpert, K.

    1998-07-01

    Released as gaseous species during coal combustion and gasification, alkali metal compounds cause high temperature corrosion especially at the gas turbine blading of coal-fired combined cycle power plants. Experimental and theoretical basic investigations are presented, which contribute to the understanding of the release and sorption of these contaminants. Knudsen effusion mass spectrometry was used to study the vaporization of coal ashes and slags at temperatures between 200 and 1,800 C and to determine the released alkali species and their partial pressures. The data base system FACT and the modified quasi-chemical model for non-ideal solutions were applied to model the thermodynamic behavior of coal slags and to determine material compositions of maximum alkali sorption capacity.

  16. Chemical compatibility of structural materials in alkali metals

    SciTech Connect

    Natesan, K.; Rink, D.L.; Haglund, R.

    1995-04-01

    The objectives of this task are to (a) evaluate the chemical compatibility of structural alloys such as V-5 wt.%Cr-5 wt.%Ti alloy and Type 316 stainless steel for application in liquid alkali metals such as lithium and sodium-78 wt.% potassium (NaK) at temperatures in the range that are of interest for International Thermonuclear Experimental Reactor (ITER); (b) evaluate the transfer of nonmetallic elements such as oxygen, nitrogen, carbon, and hydrogen between structural materials and liquid metals; and (c) evaluate the effects of such transfers on the mechanical and microstructural characteristics of the materials for long-term service in liquid-metal-environments.

  17. Wetting Transitions of Inert Gases on Alkali Metal Surfaces

    NASA Astrophysics Data System (ADS)

    Bojan, M. J.; McDonald, I. A.; Cole, M. W.; Steele, W. A.

    1996-03-01

    Theoretical and experimental discoveries have been made recently of wetting and prewetting transitions of helium and hydrogen films on alkali metal surfaces [1,2]. New experiments show anomalous nonwetting behavior of Ne on Rb and Cs [3]. Building on earlier work [4], we have done and will describe results from the first Monte Carlo simulations showing wetting transitions for classical gases on alkali metal surfaces. * Research supported by an NSF Materials Research Group grant. 1. R. B.Hallock, J. Low Temp. Phys. 101, 31, 1995 2. M. W. Cole, J. Low Temp. Phys. 101, 25, 1995. 3. G. B. Hess, M. Sabatini, and M. H. W. Chan, unpublished 4. J. E. Finn and P. A. Monson, Phys. Rev. A 39, 6402, 1989.

  18. [Measurement of Mole Ratio for Alkali Metal Mixture by Using Spectral Absorption Method].

    PubMed

    Zou, Sheng; Zhang, Hong; Chen, Yao; Chen, Xi-yuan

    2015-08-01

    The ratio of alkali metal mixture is one of the most important parameters in gauge head belonging to the ultra-sensitivity inertial measurement equipment, which is required to detect precisely. According to the feature that ratio of alkali metal is related to alkali metal vapor density, the theory of optical depth is used to detect the ratio of alkali metal in the present article. The result shows that the data got by the theory of optical depth compared with empirical formula differs at three orders of magnitude, which can't ensure the accuracy. By changing the data processing method, model between spectral absorption rate and temperature in cell is established. The temperature in alkali metal cell is calibrated by spectral absorption rate. The ratio of alkali metal atoms in the cell is analyzed by calculating the alkali density with empirical formula. The computational error is less than 10%. PMID:26672309

  19. Neutron imaging of alkali metal heat pipes

    SciTech Connect

    Kihm, Ken; Kirchoff, Eric; Golden, Matt; Rosenfeld, J.; Rawal, S.; Pratt, D.; Bilheux, Hassina Z; Walker, Lakeisha MH; Voisin, Sophie; Hussey, Dan

    2013-01-01

    High-temperature heat pipes are two-phase, capillary driven heat transfer devices capable of passively providing high thermal fluxes. Such a device using a liquid-metal coolant can be used as a solution for successful thermal management on hypersonic flight vehicles. Imaging of the liquid-metal coolant inside will provide valuable information in characterizing the detailed heat and mass transport. Neutron imaging possesses an inherent advantage from the fact that neutrons penetrate the heat pipe metal walls with very little attenuation, but are significantly attenuated by the liquid metal contained inside. Using the BT-2 beam line at the National Institute of Standards and Technology (NIST) in Gaithersburg, Maryland, preliminary efforts have been conducted on a nickel-sodium heat pipe. The contrast between the attenuated beam and the background is calculated to be approximately 3%. This low contrast requires sacrifice in spatial or temporal resolution so efforts have since been concentrated on lithium (Li) which has a substantially larger neutron attenuation cross section. Using the CG-1D beam line at the High Flux Isotope Reactor (HFIR) of Oak Ridge National Laboratory (ORNL) in Oak Ridge, Tennessee, the first neutron images of high-temperature molybdenum (Mo)-Li heat pipes have been achieved. The relatively high neutron cross section of Li allows for the visualization of the Li working fluid inside the heat pipes. The evaporator region of a gravity assisted cylindrical heat pipe prototype 25 cm long was imaged from start-up to steady state operation up to approximately 900 C. In each corner of the square bore inside, the capillary action raises the Li meniscus above the bulk Li pool in the evaporator region. As the operational temperature changes, the meniscus shapes and the bulk meniscus height also changes. Furthermore, a three-dimensional tomographic image is also reconstructed from the total of 128 projection images taken 1.4o apart in which the Li had

  20. Neutron Imaging of Alkali Metal Heat Pipes

    NASA Astrophysics Data System (ADS)

    Kihm, K.; Kirchoff, E.; Golden, M.; Rosenfeld, J.; Rawal, S.; Pratt, D.; Swanson, A.; Bilheux, H.; Walker, L.; Voisin, S.; Hussey, D. S.; Jacobson, D. L.

    High-temperature heat pipes are two-phase, capillary driven heat transfer devices capable of passively providing high thermal fluxes. Such a device using a liquid-metal coolant can be used as a solution for successful thermal management on hypersonic flight vehicles. Imaging of the liquid-metal coolant inside will provide valuable information in characterizing the detailed heat and mass transport. Neutron imaging possesses an inherent advantage from the fact that neutrons penetrate the heat pipe metal walls with very little attenuation, but are significantly attenuated by the liquid metal contained inside. Using the BT-2 beam line at the National Institute of Standards and Technology (NIST) in Gaithersburg, Maryland, preliminary efforts have been conducted on a nickel-sodium heat pipe. The contrast between the attenuated beam and the background is calculated to be approximately 3%. This low contrast requires sacrifice in spatial or temporal resolution so efforts have since been concentrated on lithium (Li) which has a substantially larger neutron attenuation cross section. Using the CG-1D beam line at the High Flux Isotope Reactor (HFIR) of Oak Ridge National Laboratory (ORNL) in Oak Ridge, Tennessee, the first neutron images of high-temperature molybdenum (Mo)-Li heat pipes have been achieved. The relatively high neutron cross section of Li allows for the visualization of the Li working fluid inside the heat pipes. The evaporator region of a gravity assisted cylindrical heat pipe prototype 25 cm long was imaged from start-up to steady state operation up to approximately 900 °C. In each corner of the square bore inside, the capillary action raises the Li meniscus above the bulk Li pool in the evaporator region. As the operational temperature changes, the meniscus shapes and the bulk meniscus height also changes. Furthermore, a three-dimensional tomographic image is also reconstructed from the total of 128 projection images taken 1.4o apart in which the Li had

  1. Raman spectroscopic investigation of alkali-metal hexachloro compounds of refractory metals

    SciTech Connect

    Kipouros, G.J.; Flint, J.H.; Sadoway, D.R.

    1985-11-06

    The Raman spectra of molten alkali-metal hexachlorozirconate, hexachlorohafnate, hexachloroniobate, and hexachlorotantalate compounds have been obtained in the temperature range 623-1143 K. The results confirm that the refractory metal exists in the form of an octahedrally coordinated complex anion that is stable even in the molten state. For a given refractory metal the frequency of the nu/sub 1/ line increases as the size of the alkali-metal cation decreases. For a given alkali metal the frequency of the nu/sub 1/ line increases as the valence of the refractory metal increases. This last observation may serve as the basis for detecting, by Raman spectroscopy, aliovalent species that may form during the electrolysis of melts containing refractory-metal chlorides. 22 references, 4 figures, 2 tables.

  2. Process for carbonaceous material conversion and recovery of alkali metal catalyst constituents held by ion exchange sites in conversion residue

    DOEpatents

    Sharp, David W.

    1980-01-01

    In a coal gasification operation or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein solid particles containing alkali metal residues are produced, alkali metal constituents are recovered for the particles by contacting or washing them with an aqueous solution containing calcium or magnesium ions in an alkali metal recovery zone at a low temperature, preferably below about 249.degree. F. During the washing or leaching process, the calcium or magnesium ions displace alkali metal ions held by ion exchange sites in the particles thereby liberating the ions and producing an aqueous effluent containing alkali metal constituents. The aqueous effluent from the alkali metal recovery zone is then recycled to the conversion process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst.

  3. Metal silicate mixtures - Spectral properties and applications to asteroid taxonomy

    NASA Technical Reports Server (NTRS)

    Cloutis, Edward A.; Smith, Dorian G. W.; Lambert, Richard St. J.; Gaffey, Michael J.

    1990-01-01

    The reflectance spectra of combinations of olivine, orthopyroxene, and iron meteorite metal are experimentally studied, and the obtained variations in spectral properties are used to constrain the physical and chemical properties of the assemblages. The presence of metal most noticeably affects band area ratios, peak-to-peak and peak-to-minimum reflectance ratios, and band widths. Band width and band areas are useful for determining metal abundance in olivine and metal and orthopyroxene and metal assemblages, respectively. Mafic silicate grain size variations are best determined using band depth criteria. Band centers are most useful for determining mafic silicate composition. An application of these parameters to the S-class asteroid Flora is presented.

  4. Estimation of high temperature metal-silicate partition coefficients

    NASA Technical Reports Server (NTRS)

    Jones, John H.; Capobianco, Christopher J.; Drake, Michael J.

    1992-01-01

    It has been known for some time that abundances of siderophile elements in the upper mantle of the Earth are far in excess of those expected from equilibrium between metal and silicate at low pressures and temperatures. Murthy (1991) has re-examined this excess of siderophile element problem by estimating liquid metal/liquid silicate partition coefficients reduces from their measured values at a lower temperature, implying that siderophile elements become much less siderophilic at high temperatures. Murthy then draws the important conclusion that metal/silicate equilibrium at high temperatures can account for the abundances of siderophile elements in the Earth's mantle. Of course, his conclusion is critically dependent on the small values of the partition coefficients he calculates. Because the numerical values of most experimentally-determined partition coefficients increase with increasing temperature at both constant oxygen fugacity and at constant redox buffer, we think it is important to try an alternative extrapolation for comparison. We have computed high temperature metal/silicate partition coefficients under a different set of assumptions and show that such long temperature extrapolations yield values which are critically dependent upon the presumed chemical behavior of the siderophile elements in the system.

  5. Alkali activation of recovered fuel-biofuel fly ash from fluidised-bed combustion: Stabilisation/solidification of heavy metals.

    PubMed

    Yliniemi, Juho; Pesonen, Janne; Tiainen, Minna; Illikainen, Mirja

    2015-09-01

    Recovered fuel-biofuel fly ash from a fluidized bed boiler was alkali-activated and granulated with a sodium-silicate solution in order to immobilise the heavy metals it contains. The effect of blast-furnace slag and metakaolin as co-binders were studied. Leaching standard EN 12457-3 was applied to evaluate the immobilisation potential. The results showed that Ba, Pb and Zn were effectively immobilised. However, there was increased leaching after alkali activation for As, Cu, Mo, Sb and V. The co-binders had minimal or even negative effect on the immobilisation. One exception was found for Cr, in which the slag decreased leaching, and one was found for Cu, in which the slag increased leaching. A sequential leaching procedure was utilized to gain a deeper understanding of the immobilisation mechanism. By using a sequential leaching procedure it is possible fractionate elements into watersoluble, acid-soluble, easily-reduced and oxidisable fractions, yielding a total 'bioavailable' amount that is potentially hazardous for the environment. It was found that the total bioavailable amount was lower following alkali activation for all heavy metals, although the water-soluble fraction was higher for some metals. Evidence from leaching tests suggests the immobilisation mechanism was chemical retention, or trapping inside the alkali activation reaction products, rather than physical retention, adsorption or precipitation as hydroxides. PMID:26054963

  6. Alkali metals conductivity at multistep dynamic compression

    NASA Astrophysics Data System (ADS)

    Postnov, Victor I.

    2005-07-01

    This work is devoted to studying of phase and structural transitions, in alkaline metals (lithium, sodium, potassium and calcium) at dynamic compression. Experiments were carried out at a room temperature and at temperature of liquid nitrogen with application of smooth shock wave technique. As a result for calcium almost tenfold increase in electrical resistance was observed at the maximal pressure 60GPa. Similar electrical resistance changing was fixed in sodium experiments. In experiments with lithium the range of pressure has been expanded up to 210GPa. The break on pressure-resistivity dependence at 160Gpa was found [1]. The fixed electrical resistance changing of samples at 120GPa makes about 70 times. Character of pressure-resistivity dependence for potassium samples qualitatively coincides with fixed for sodium and lithium. In unloading electrical resistance of all samples came back to the initial value. This phenomenon testified about convertibility of occurring processes. This work was supported by RFBR N03-02-16322, grant of the President of Russia N NS 1938.2003.2, program of basic researches of the Russian Academy of Science ``Thermophysics and mechanics of intensive energy influences'' and Russian Science Support Foundation. 1. V E Fortov, V V Yakushev, K l Kagan et al // J.Phys.: Condens Matter 14 (2002) 10809-10816

  7. Compliant alkali silicate sealing glass for solid oxide fuel cell applications: Combined stability in isothermal ageing and thermal cycling with YSZ coated ferritic stainless steels

    NASA Astrophysics Data System (ADS)

    Chou, Yeong-Shyung; Thomsen, E. C.; Choi, J.-P.; Stevenson, J. W.

    2012-01-01

    An alkali silicate glass (SCN-1) is being evaluated as a candidate sealant for solid oxide fuel cell (SOFC) applications. The glass contains about 17 wt.% alkalis (K + Na) and has low glass transition and softening temperatures. It remains vitreous and compliant after sealing without substantial crystallization, as contrary to conventional glass-ceramic sealant. The glassy nature and low characteristic temperatures can reduce residual stresses and result in the potential for crack healing. In a previous study, the glass was found to have good thermal cycle stability and was chemically compatible with yttria stabilized zirconia (YSZ) coating during short term testing. In this study, the compliant glass was further evaluated in a more realistic way in that the sealed couples were first isothermally aged for 1000 h followed by thermal cycling. High temperature leakage was measured. Chemical compatibility was also investigated with powder mixtures to enhance potential interfacial reaction. In addition, interfacial microstructure was examined with scanning electron microscopy and evaluated with regard to the leakage and chemical compatibility results. Overall the compliant sealing glass showed desirable chemical compatibility with YSZ coated metallic interconnect of minimum reaction and hermetic behavior at 700-750 °C in dual environment.

  8. Metal/Silicate Partitioning at High Pressures and Temperatures

    NASA Technical Reports Server (NTRS)

    Shofner, G.; Campbell, A.; Danielson, L.; Righter, K.; Rahman, Z.

    2010-01-01

    The behavior of siderophile elements during metal-silicate segregation, and their resulting distributions provide insight into core formation processes. Determination of partition coefficients allows the calculation of element distributions that can be compared to established values of element abundances in the silicate (mantle) and metallic (core) portions of the Earth. Moderately siderophile elements, including W, are particularly useful in constraining core formation conditions because they are sensitive to variations in T, P, oxygen fugacity (fO2), and silicate composition. To constrain the effect of pressure on W metal/silicate partitioning, we performed experiments at high pressures and temperatures using a multi anvil press (MAP) at NASA Johnson Space Center and laser-heated diamond anvil cells (LHDAC) at the University of Maryland. Starting materials consisted of natural peridotite mixed with Fe and W metals. Pressure conditions in the MAP experiments ranged from 10 to 16 GPa at 2400 K. Pressures in the LHDAC experiments ranged from 26 to 58 GPa, and peak temperatures ranged up to 5000 K. LHDAC experimental run products were sectioned by focused ion beam (FIB) at NASA JSC. Run products were analyzed by electron microprobe using wavelength dispersive spectroscopy. Liquid metal/liquid silicate partition coefficients for W were calculated from element abundances determined by microprobe analyses, and corrected to a common fO2 condition of IW-2 assuming +4 valence for W. Within analytical uncertainties, W partitioning shows a flat trend with increasing pressure from 10 to 16 GPa. At higher pressures, W becomes more siderophile, with an increase in partition coefficient of approximately 0.5 log units.

  9. Laboratory studies of actinide metal-silicate fractionation

    NASA Technical Reports Server (NTRS)

    Jones, J. H.; Burnett, D. S.

    1980-01-01

    Actinide and Sm partition coefficients between silicate melt and several metallic phases have been measured. Under reducing conditions Si, Th, U and Pu can be reduced to metals from silicate melts and alloyed with a platinum-gold alloy. U and Pu enter a molten Pt-Si alloy with roughly equal affinity but U strongly partitions into the solid Pt. Th behaves qualitatively the same as Pu but is much less readily reduced than U, and Sm appears to remain unreduced. Experiments with Fe metal have shown that the partition coefficients of the actinides between Fe and silicate liquid are extremely low, suggesting a very low actinide concentration in planetary cores. Experiments show that platinum metals can efficiently fractionate actinides and fractionate actinides from lanthanides and this process may be relevant to the condensation behavior of these elements from the solar nebula. Pt-metal grains in Allende Ca-Al-rich inclusions appear to be U-poor, although the sub-class of Zr-bearing Pt metals may have high U contents.

  10. Metal silicate relationships in Apollo 17 soils

    NASA Technical Reports Server (NTRS)

    Goldstein, J. I.; Hewins, R. H.; Axon, H. J.

    1974-01-01

    A petrographic, metallographic, and electron probe study of particles from two Apollo 17 soils is reported. A mixing model for the formation of the Apollo 17 soils is proposed. It is found that equilibration temperatures for two-phase metal aggregates range from 375 to 475 C for metal-phosphide particles and from 480 to 630 C for alpha-gamma particles, and that the anorthositic soil particles contain metal of meteoritic Ni-Co content. The Camelot Crater and the Sculptured Hills soil compositions are discussed.

  11. Dirac Node Lines in Pure Alkali Earth Metals.

    PubMed

    Li, Ronghan; Ma, Hui; Cheng, Xiyue; Wang, Shoulong; Li, Dianzhong; Zhang, Zhengyu; Li, Yiyi; Chen, Xing-Qiu

    2016-08-26

    Beryllium is a simple alkali earth metal, but has been the target of intensive studies for decades because of its unusual electron behavior at surfaces. The puzzling aspects include (i) severe deviations from the description of the nearly free-electron picture, (ii) an anomalously large electron-phonon coupling effect, and (iii) giant Friedel oscillations. The underlying origins for such anomalous surface electron behavior have been under active debate, but with no consensus. Here, by means of first-principles calculations, we discover that this pure metal system, surprisingly, harbors the Dirac node line (DNL) that in turn helps to rationalize many of the existing puzzles. The DNL is featured by a closed line consisting of linear band crossings, and its induced topological surface band agrees well with previous photoemission spectroscopy observations on the Be (0001) surface. We further reveal that each of the elemental alkali earth metals of Mg, Ca, and Sr also harbors the DNL and speculate that the fascinating topological property of the DNL might naturally exist in other elemental metals as well. PMID:27610865

  12. The Relationship Between Metal and Silicates in Type I Chondrules

    NASA Astrophysics Data System (ADS)

    Hewins, R. H.; Zanda, B.

    1992-07-01

    There is wide agreement that chondrules were formed by melting of pre-existing minerals, but there is still controversy over how, when, and from exactly what they were formed. Much work on chondrules has emphasized magnesian granular/microporphyritic type I chondrules, but metal-rich type I chondrules are even more abundant in carbonaceous chondrites (McSween, 1977). The observation that metal is homogeneous within one chondrule but differs from chondrule to chondrule (Zanda et al., 1991) suggests some systematic relationship may exist between metal and silicates. It is the purpose of this paper to investigate those relationships for Renazzo and Semarkona. We observe a strong correlation between the silicate texture of chondrules, which falls in a fine-coarse granular-porphyritic-barred sequence related to degree of melting, and the nature of the metal. Where olivine grains are small and/or closely packed, metal occurs as tiny spherules. Where grain size and melt channels are larger, metal forms coalescing blebs or chains. With distinctly microporphyritic textures metal occurs mostly near the periphery of the chondrule and with truly porphyritic and barred chondrules it forms a rim or crown around the chondrule. Similar metal coalescence and expulsion textures have been observed for Bishunpur chondrules (Rambaldi and Wasson, 1981) and geochemical evidence shows that metal rims on Semarkona chondrules were derived from their interiors (Grossman and Wasson, 1987). There appears to be a continuous gradation between metal-rich and ordinary type I chondrules as a function of degree of melting, which suggests that many type I chondrules passed through a stage of being metal-rich during formation. If chondrules were manufactured from homogeneous interstellar dust, there is a very short time period for metal-silicate fractionation. If chondrules were formed from condensate aggregates, this constraint can be relaxed as condensates aggregated over different temperature

  13. Efficient destruction of CF4 through in situ generation of alkali metals from heated alkali halide reducing mixtures.

    PubMed

    Lee, Myung Churl; Choi, Wonyong

    2002-03-15

    Perfluorocarbons (PFCs) are the most potent green house gases that are very recalcitrant at destruction. An effective way of converting PFCs using hot solid reagents into safe products has been recently introduced. By investigating the thermal reductive destruction of tetrafluoromethane (CF4) we provided new insight and more physicochemical consideration on this novel process. The complete destruction of CF4was successfully achieved by flowing the gas through a heated reagent bed (400-950 degrees C) that contained powder mixtures of alkali halides, CaO, and Si. The silicon acted as a reducing agent of alkali halides for the in-situ production of alkali metals, and the calcium oxide played the role of a halide ion acceptor. The absence of any single component in this ternary mixture drastically reduced the destruction efficiency of CF4. The CF4 destruction efficiencies with the solid reagent containing the alkali halide, MX, increased in the order of Li approximately Na < K < Cs for alkali cations and I < Br < Cl < F for halide anions. This trend agreed with the endothermicity of the alkali metal generation reaction: the higher the endothermicity, the lower the destruction efficiency. Alkali metal generation was indirectly detected by monitoring H2 production from its reaction with water. The production of alkali metals increased with NaF, KF, and CsF in this order. The CsF/CaO/Si system exhibited the complete destruction of CF4 at as low as 600 degrees C. The solid product analysis by X-ray diffraction (XRD) showed the formation of CaF2 and the depletion of Si with black carbon particles formed in the solid reagent residue. No CO/CO2 and toxic HF and SiF4 formation were detected in the exhaust gas. PMID:11944694

  14. 40 CFR 721.4663 - Fluorinated carboxylic acid alkali metal salts.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... metal salts. 721.4663 Section 721.4663 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4663 Fluorinated carboxylic acid alkali metal salts. (a) Chemical... fluorinated carboxylic acid alkali metal salts (PMNs P-95-979/980/981) are subject to reporting under...

  15. 40 CFR 721.10097 - Disubstituted benzenesulfonic acid, alkali metal salt (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., alkali metal salt (generic). 721.10097 Section 721.10097 Protection of Environment ENVIRONMENTAL... metal salt (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as disubstituted benzenesulfonic acid, alkali metal salt (PMN...

  16. 40 CFR 721.10097 - Disubstituted benzenesulfonic acid, alkali metal salt (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., alkali metal salt (generic). 721.10097 Section 721.10097 Protection of Environment ENVIRONMENTAL... metal salt (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as disubstituted benzenesulfonic acid, alkali metal salt (PMN...

  17. 40 CFR 721.4663 - Fluorinated carboxylic acid alkali metal salts.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... metal salts. 721.4663 Section 721.4663 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4663 Fluorinated carboxylic acid alkali metal salts. (a) Chemical... fluorinated carboxylic acid alkali metal salts (PMNs P-95-979/980/981) are subject to reporting under...

  18. 40 CFR 721.10098 - Disubstituted benzoic acid, alkali metal salt (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... metal salt (generic). 721.10098 Section 721.10098 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.10098 Disubstituted benzoic acid, alkali metal salt... identified generically as disubstituted benzoic acid, alkali metal salt (PMN P-03-643) is subject...

  19. 40 CFR 721.10098 - Disubstituted benzoic acid, alkali metal salt (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... metal salt (generic). 721.10098 Section 721.10098 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.10098 Disubstituted benzoic acid, alkali metal salt... identified generically as disubstituted benzoic acid, alkali metal salt (PMN P-03-643) is subject...

  20. 40 CFR 721.10098 - Disubstituted benzoic acid, alkali metal salt (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... metal salt (generic). 721.10098 Section 721.10098 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.10098 Disubstituted benzoic acid, alkali metal salt... identified generically as disubstituted benzoic acid, alkali metal salt (PMN P-03-643) is subject...

  1. 40 CFR 721.4663 - Fluorinated carboxylic acid alkali metal salts.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... metal salts. 721.4663 Section 721.4663 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4663 Fluorinated carboxylic acid alkali metal salts. (a) Chemical... fluorinated carboxylic acid alkali metal salts (PMNs P-95-979/980/981) are subject to reporting under...

  2. 40 CFR 721.10098 - Disubstituted benzoic acid, alkali metal salt (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... metal salt (generic). 721.10098 Section 721.10098 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.10098 Disubstituted benzoic acid, alkali metal salt... identified generically as disubstituted benzoic acid, alkali metal salt (PMN P-03-643) is subject...

  3. 40 CFR 721.4663 - Fluorinated carboxylic acid alkali metal salts.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... metal salts. 721.4663 Section 721.4663 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4663 Fluorinated carboxylic acid alkali metal salts. (a) Chemical... fluorinated carboxylic acid alkali metal salts (PMNs P-95-979/980/981) are subject to reporting under...

  4. 40 CFR 721.10097 - Disubstituted benzenesulfonic acid, alkali metal salt (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ..., alkali metal salt (generic). 721.10097 Section 721.10097 Protection of Environment ENVIRONMENTAL... metal salt (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as disubstituted benzenesulfonic acid, alkali metal salt (PMN...

  5. 40 CFR 721.10097 - Disubstituted benzenesulfonic acid, alkali metal salt (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ..., alkali metal salt (generic). 721.10097 Section 721.10097 Protection of Environment ENVIRONMENTAL... metal salt (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as disubstituted benzenesulfonic acid, alkali metal salt (PMN...

  6. Substitution mechanism of alkali metals for strontium in strontium hydroxyapatite

    SciTech Connect

    Naddari, Thouraya; Hamdi, Besma; Savariault, Jean Michel; El Feki, Hafed; Ben Salah, Abdelhamid

    2003-01-25

    Strontium hydroxyapatites substituted by alkali metals are synthesized by double decomposition method in basic medium. Structures of Sr{sub 9.50}Na{sub 0.30}(PO{sub 4}){sub 6}(OH){sub 1.30} (SrNaHAp) and Sr{sub 9.81}K{sub 0.12}(PO{sub 4}){sub 6}(OH){sub 1.74} (SrKHAp) are determined by X-ray powder diffraction. Both compounds are isotypic and crystallize in hexagonal system (space group P63/m) with the following cells: a=9.751(3) A and c=7.279(3) A for SrNaHAp and a=9.755(4) A and c=7.284(3) A for SrKHAp. Results are compared to those of Sr{sub 10}(PO{sub 4}){sub 6}(OH){sub 2}. According to the site occupancy factors, in SrNaHAp sodium is localized in site (I) and in SrKHAp potassium in site (II). Both structures contain vacancies in hydroxyl and metal sites. The mechanism of alkali metals substitution for strontium proposed explains the vacancies formation.

  7. Magnetic Resonance Reversals in Optically Pumped Alkali-Metal Vapor

    NASA Astrophysics Data System (ADS)

    Gong, Fei; Jau, Yuan-Yu; Happer, William

    2007-06-01

    We report an unusual new phenomenon, peculiar sign reversals of the ground-state magnetic resonances and of the ``zero-dip" resonance (Zeeman resonance at zero field) of optically-pumped, alkali-metal vapors. These anomalies occur when a ``weak" circular polarized D1 laser light is tuned to pump atoms predominantly from the lower ground-state hyperfine multiplet. One can understand the signal reversals in simple, semi-quantitative way with reference to this distribution. uantitative computer simulations are in excellent greement with observations.

  8. Magnetic resonance reversals in optically pumped alkali-metal vapor

    NASA Astrophysics Data System (ADS)

    Gong, F.; Jau, Y.-Y.; Happer, W.

    2007-05-01

    We report an unusual phenomenon, peculiar sign reversals of the ground-state magnetic resonances and of the zero-dip resonance (Zeeman resonance at zero field) of optically pumped, alkali-metal vapors. These anomalies occur when a weak circularly polarized D1 laser light is tuned to pump atoms predominantly from the lower ground-state hyperfine multiplet. One can understand the signal reversals in a simple, semiquantitative way with reference to the spin-temperature distribution. Quantitative computer simulations are in excellent agreement with observations.

  9. Alkali metal/halide thermal energy storage systems performance evaluation

    NASA Technical Reports Server (NTRS)

    Phillips, W. M.; Stearns, J. W.

    1986-01-01

    A pseudoheat-pipe heat transfer mechanism has been demonstrated effective in terms of both total heat removal efficiency and rate, on the one hand, and system isothermal characteristics, on the other, for solar thermal energy storage systems of the kind being contemplated for spacecraft. The selection of appropriate salt and alkali metal substances for the system renders it applicable to a wide temperature range. The rapid heat transfer rate obtainable makes possible the placing of the thermal energy storage system around the solar receiver canister, and the immersing of heat transfer fluid tubes in the phase change salt to obtain an isothermal heat source.

  10. Optical response of alkali metal atoms confined in nanoporous glass

    SciTech Connect

    Burchianti, A; Marinelli, C; Mariotti, E; Bogi, A; Marmugi, L; Giomi, S; Maccari, M; Veronesi, S; Moi, L

    2014-03-28

    We study the influence of optical radiation on adsorption and desorption processes of alkali metal atoms confined in nanoporous glass matrices. Exposure of the sample to near-IR or visible light changes the atomic distribution inside the glass nanopores, forcing the entire system to evolve towards a different state. This effect, due to both atomic photodesorption and confinement, causes the growth and evaporation of metastable nanoparticles. It is shown that, by a proper choice of light characteristics and pore size, these processes can be controlled and tailored, thus opening new perspectives for fabrication of nanostructured surfaces. (nanoobjects)

  11. Nuclear alkali metal Rankine power systems for space applications

    SciTech Connect

    Moyers, J.C.; Holcomb, R.S.

    1986-08-01

    Nucler power systems utilizing alkali metal Rankine power conversion cycles offer the potential for high efficiency, lightweight space power plants. Conceptual design studies are being carried out for both direct and indirect cycle systems for steady state space power applications. A computational model has been developed for calculating the performance, size, and weight of these systems over a wide range of design parameters. The model is described briefly and results from parametric design studies, with descriptions of typical point designs, are presented in this paper.

  12. Theoretical determination of the alkali-metal superoxide bond energies

    NASA Technical Reports Server (NTRS)

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

    1992-01-01

    The bond dissociation energies for the alkali-metal superoxides have been computed using extensive Gaussian basis sets and treating electron correlation at the modified coupled-pair functional level. Our computed D0 values are 61.4, 37.2, 40.6, and 38.4 kcal/mol for LiO2, NaO2, KO2, and RbO2, respectively. These values, which are expected to be lower bounds and accurate to 2 kcal/mol, agree well with some of the older flame data, but rule out several recent experimental measurements.

  13. Laser synthesis of ultracold alkali metal dimers: optimization and control

    NASA Astrophysics Data System (ADS)

    Pazyuk, E. A.; Zaitsevskii, A. V.; Stolyarov, A. V.; Tamanis, M.; Ferber, R.

    2015-10-01

    The review concerns the potential of modern high-resolution laser spectroscopy and state-of-the-art ab initio electronic structure calculations used to obtain comprehensive information on the energy and radiative properties of strongly coupled rovibronic diatomic states. The possibility of deperturbation treatment of the intermediate electronically excited states at the experimental (spectroscopic) level of accuracy is demonstrated taking alkali metal dimers as examples. The deperturbation analysis is of crucial importance to optimize multistep laser synthesis and stabilization of ultracold molecular ensembles in their absolute ground level. The bibliography includes 227 references.

  14. An Alkali Metal-Capped Cerium(IV) Imido Complex.

    PubMed

    Solola, Lukman A; Zabula, Alexander V; Dorfner, Walter L; Manor, Brian C; Carroll, Patrick J; Schelter, Eric J

    2016-06-01

    Structurally authenticated, terminal lanthanide-ligand multiple bonds are rare and expected to be highly reactive. Even capped with an alkali metal cation, poor orbital energy matching and overlap of metal and ligand valence orbitals should result in strong charge polarization within such bonds. We expand on a new strategy for isolating terminal lanthanide-ligand multiple bonds using cerium(IV) complexes. In the current case, our tailored tris(hydroxylaminato) ligand framework, TriNOx(3-), provides steric protection against ligand scrambling and metal complex oligomerization and electronic protection against reduction. This strategy culminates in isolation of the first formal Ce═N bonded moiety in the complex [K(DME)2][Ce═N(3,5-(CF3)2C6H3)(TriNOx)], whose Ce═N bond is the shortest known at 2.119(3) Å. PMID:27163651

  15. Nonlinear pressure shifts of alkali-metal atoms in xenon

    NASA Astrophysics Data System (ADS)

    McGuyer, Bart; Xia, Tian; Jau, Yuan-Yu; Happer, William

    2011-05-01

    Compact, portable atomic frequency standards are based on the microwave resonance frequencies of alkali-metal atoms in inert buffer gases. The frequency shift of these resonances due to collisions with the buffer gas is known as the pressure shift. We demonstrate that the microwave resonance frequencies of ground-state 87Rb and 133Cs atoms have a nonlinear dependence on the pressure of the buffer gas Xe. Previous work has demonstrated a nonlinear dependence in Ar and Kr, but not He and N2, which is thought to be due to the loosely-bound van der Waals molecules that are known to form between alkali-metal and buffer-gas atoms in Ar, Kr, and Xe, but not He and N2. Surprisingly, we find that the nonlinearities in Xe are of the opposite sign to those in Ar and Kr, even though the overall shifts for each of these gases are negative. This discrepancy suggests that though the shifts due to the molecules in Ar and Kr are positive, the shifts due to the molecules in Xe are negative. No nonlinearities were observed in the buffer gas Ne to within our experimental accuracy, which suggests that molecules do not form in Ne. Additionally, we present improved measurements of the shifts of Rb and Cs in He and N2 and of Rb in Ar and Kr. This work was supported by the Air Force Office of Scientific Research and the Department of Defense through the NDSEG program.

  16. Universalities in ultracold reactions of alkali-metal polar molecules

    NASA Astrophysics Data System (ADS)

    Quéméner, Goulven; Bohn, John L.; Petrov, Alexander; Kotochigova, Svetlana

    2011-12-01

    We consider ultracold collisions of ground-state heteronuclear alkali-metal dimers that are susceptible to four-center chemical reactions 2AB→A2+B2 even at submicrokelvin temperatures. These reactions depend strongly on species, temperature, electric field, and confinement in an optical lattice. We calculate ab initio van der Waals coefficients for these interactions and use a quantum formalism to study the scattering properties of such molecules under an external electric field and optical lattice. We also apply a quantum threshold model to explore the dependence of reaction rates on the various parameters. We find that, among the heteronuclear alkali-metal fermionic species, LiNa is the least reactive, whereas LiCs is the most reactive. For the bosonic species, LiK is the most reactive in zero field, but all species considered, LiNa, LiK, LiRb, LiCs, and KRb, share a universal reaction rate once a sufficiently high electric field is applied. For indistinguishable bosons, the inelastic/reactive rate increases as d2 in the quantum regime, where d is the dipole moment induced by the electric field. This is a weaker power-law dependence than for indistinguishable fermions, for which the rate behaves as d6.

  17. Identifying alkali metal inhibitors of crystal growth: a selection criterion based on ion pair hydration energy.

    PubMed

    Farmanesh, Sahar; Alamani, Bryan G; Rimer, Jeffrey D

    2015-09-21

    We show that alkali metals function as effective modifiers of calcium oxalate monohydrate (COM) crystallization wherein alkali-oxalate ion parings reduce the rate of crystal growth by as much as 60%. Our findings reveal a distinct trend in alkali metal efficacy that cannot be explained by colloidal theories or simple descriptors, such as ion size, but is consistent with a theoretical model that accounts for the ion pair's affinity for water. PMID:26242310

  18. Compliant alkali silicate sealing glass for solid oxide fuel cell applications: thermal cycle stability and chemical compatibility

    SciTech Connect

    Chou, Y. S.; Thomsen, Edwin C.; Williams, Riley T.; Choi, Jung-Pyung; Canfield, Nathan L.; Bonnett, Jeff F.; Stevenson, Jeffry W.; Shyam, Amit; Lara-Curzio, E.

    2011-03-01

    An alkali silicate glass (SCN-1) is currently being evaluated as a candidate sealing glass for solid oxide fuel (SOFC) applications. The glass containing ~17 mole% alkalis (K2O and Na2O) remains vitreous and compliant during SOFC operation, unlike conventional SOFC sealing glasses, which experience substantial devitrification after the sealing process. The non-crystallizing compliant sealing glass has lower glass transition and softening temperatures since the microstructure remains glassy without significant crystallite formation, and hence can relieve or reduce residual stresses and also has the potential for crack healing. Sealing approaches based on compliant glass will also need to satisfy all the mechanical, thermal, chemical, physical, and electrical requirements for SOFC applications, not only in bulk properties but also at sealing interfaces. In this first of a series of papers we will report the thermal cycle stability of the glass when sealed between two SOFC components, i.e., a NiO/YSZ anode supported YSZ bilayer and a coated ferritic stainless steel interconnect material. High temperature leak rates were monitored versus thermal cycles between 700-850oC using back pressures ranging from 0.2 psi to 1.0 psi. Isothermal stability was also evaluated in a dual environment consisting of flowing dilute H2 fuel versus ambient air. In addition, chemical compatibility at the alumina and YSZ interfaces was examined with scanning electron microscopy and energy dispersive spectroscopy. The results shed new light on the topic of SOFC glass seal development.

  19. Theoretical investigations on the stability of alkali metal substituted phenylpentazole.

    PubMed

    Zhang, Xueli; Gong, Xuedong

    2016-05-01

    The alkali metal (M=Li, Na, and K) para-substituted (M-1), meta-substituted (M-2) or ortho-substituted (M-3) derivatives of phenylpentazole (PhN5) were studied using density functional theory. The substituted metals improve the energy barrier for decomposition of the N5 ring of PhN5 by 19.3 ∼ 65.0 kJ/mol. M-3 has the ionic N-M bond, which is not found for M-1 and M-2. M-1 and M-2 have similar electrostatic potentials and dispersion interactions between metal and N5 ring. The comparable intramolecular interactions of M-1 and M-2 lead to similar N5 ring stability. Compared to M-1 and M-2, M-3 has a more negative charge on N5 ring and stronger dispersion interaction. The stronger intramolecular interactions of M-3 result in the higher N5 ring stability. For M-1 and M-2, different metals have slight affects on N5 ring stability. For M-3, N5 ring stability decreases in the order of Li > Na > K. The substituted metal lowers E g of PhN5. PMID:27083566

  20. Difficulties in Interpreting Alkali Metal Trends at the Senior Chemistry Level.

    ERIC Educational Resources Information Center

    de Berg, Kevin

    2001-01-01

    Explores the reasons for the differences in alkali metal reactivity in water in terms of thermodynamics rather than ionization trends. Shows that differences in alkali metal reactivity with water are more appropriately explained in terms of the kinetics of the reactions. (MM)

  1. 40 CFR 721.5452 - Alkali metal salt of halogenated organoborate (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.5452 Alkali metal salt of halogenated organoborate (generic). (a... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkali metal salt of...

  2. 40 CFR 721.5985 - Fatty alkyl phosphate, alkali metal salt (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... salt (generic). 721.5985 Section 721.5985 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.5985 Fatty alkyl phosphate, alkali metal salt (generic). (a) Chemical... as a fatty alkyl phosphate, alkali metal salt (PMN P-99-0385) is subject to reporting under...

  3. 40 CFR 721.5985 - Fatty alkyl phosphate, alkali metal salt (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... salt (generic). 721.5985 Section 721.5985 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.5985 Fatty alkyl phosphate, alkali metal salt (generic). (a) Chemical... as a fatty alkyl phosphate, alkali metal salt (PMN P-99-0385) is subject to reporting under...

  4. 40 CFR 721.5985 - Fatty alkyl phosphate, alkali metal salt (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... salt (generic). 721.5985 Section 721.5985 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.5985 Fatty alkyl phosphate, alkali metal salt (generic). (a) Chemical... as a fatty alkyl phosphate, alkali metal salt (PMN P-99-0385) is subject to reporting under...

  5. 40 CFR 721.10097 - Disubstituted benzenesulfonic acid, alkali metal salt (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES... metal salt (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as disubstituted benzenesulfonic acid, alkali metal salt (PMN...

  6. Negative electrodes for non-aqueous secondary batteries composed on conjugated polymer and alkali metal alloying or inserting material

    SciTech Connect

    Shacklette, L.W.; Jow, T.R.; Toth, E.; Maxfield, M.

    1987-05-26

    A battery is described comprising: an anode comprising as the anode active materials one or more conjugated backbone polymers and one or more electroactive materials selected from the group consisting of metals which alloy with alkali metals and alkali metal cation inserting materials; an electrolyte comprising an organic solvent and an alkali-metal salt, and a cathode. The alkali-metal cations from the electrolyte are inserted into the anode as a metal alloy or as an inserted ion in the alkali metal cation inserting material during the charging of the battery.

  7. Investigating Metallization in Shock-Compressed Alkali Halides

    NASA Astrophysics Data System (ADS)

    Diamond, M. R.; Ali, S. J.; Eggert, J.; Jeanloz, R.; Collins, G. W.; McWilliams, R. S.

    2014-12-01

    Laser-shock compression on four alkali halides has been used to probe the transition from insulating to metallic states, a high-pressure transition in chemical bonding that has fundamental implications for planetary formation and structure. Collectively, pressures up to 450 GPa were explored across a total of fourteen single-crystal samples of CsI, CsBr, KBr and NaCl. Velocity interferometry (VISAR) was used to record shock velocities and reflectivities at 532 nm during decaying shock compression. The data show up to three-fold increases in density as well as significant increases in optical reflectivity in response to high pressures and temperatures. Using a Drude model to estimate conductivities from the measured reflectivities, we investigate the onset of metallic conductivities for each compound. Ionic salts are simple model systems amenable to first-principles theory and serve as analog materials for predicting whether specific chemical constituents can reside in the rocky mantles or metallic cores of planets. A key objective is to disentangle the complementary roles of temperature and compression in transforming ionic into metallic bonding. Furthermore, at high pressures CsI becomes analogous to Xe: they are isoelectronic and follow matching equations of state. Therefore, studies on CsI can inform understanding of noble-gas geochemistry at conditions deep inside planets (e.g., the likelihood of Xe solubility in planetary mantles or cores). Our experiments were conducted using the Janus laser of the Jupiter Laser Facility at Lawrence Livermore National Laboratory.

  8. Faraday rotation density measurements of optically thick alkali metal vapors

    NASA Astrophysics Data System (ADS)

    Vliegen, E.; Kadlecek, S.; Anderson, L. W.; Walker, T. G.; Erickson, C. J.; Happer, William

    2001-03-01

    We investigate the measurement of alkali number densities using the Faraday rotation of linearly polarized light. We find that the alkali number density may be reliably extracted even in regimes of very high buffer gas pressure, and very high alkali number density. We have directly verified our results in potassium using absorption spectroscopy on the second resonance (4 2S→5 2P).

  9. Superconductivity in the alkali metal intercalates of molybdenum disulphide

    NASA Technical Reports Server (NTRS)

    Somoano, R. B.; Hadek, V.; Rembaum, A.

    1972-01-01

    The complete series of alkali metals, lithium through cesium, have been intercalated into molybdenum disulphide, using both the liquid ammonia and vapor techniques. All the intercalates with the exception of lithium yielded full superconducting transitions with onset temperatures of 6 K for AxMoS2(Ax=K,Rb,Cs) and 4 K for BxMoS2(Bx=Li,Na). The superconducting transition for lithium was incomplete down to 1.5 K. Stoichiometries and unit cell parameters have been determined for the intercalation compounds. Both rhombohedral and hexagonal polymorphs of MoS2 have been intercalated and found to exhibit the same superconductivity behavior. The nature of the extraneous superconducting transition of some intercalated samples on exposure to air was elucidated.

  10. Mechanical stiffening and thermal softening of superionic alkali metal oxides

    NASA Astrophysics Data System (ADS)

    Chaudhary, S.; Shriya, S.; Kumar, J.; Ameri, M.; Varshney, Dinesh

    2015-06-01

    The mechanical (pressure) and thermal (temperature) dependent nature of superionic cubic M2O (M = Li, Na, K, and Rb) alkali metal oxides is studied. The model Hamiltonian in ab initio theory include long-range Coulomb, charge transfer, covalency, van der Waals interaction and the short-range repulsive interaction upto second-neighbor ions. The second order elastic constants as functions of pressure discern increasing trend, while to that they decreases with enhanced temperature. From the knowledge of elastic constants, Pugh ratio, Poisson's ratio, heat capacity and thermal expansion coefficient are calculated. It is noticed that cubic M2O is brittle on applied pressure and temperature and mechanically stiffened as a consequence of bond compression and bond strengthening and thermally softened due to bond expansion and bond weakening due to lattice vibrations.

  11. Generalized oscillator strengths and photoionization of alkali-metal atoms

    NASA Astrophysics Data System (ADS)

    Tiwary, S. N.; Nicolaides, C. A.

    1984-10-01

    Calculations of the continuum generalized oscillator strengths (CGOS) for ns → kp dipole transitions as a function of the momentum transfer K and the photoionization cross sections σ nl of the light alkali-metal atoms (Li, Na and K, with n = 2, 3, 4 respectively) have been performed within the framework of the first Born approximation (FBA) and the Vainshtein approximation (VPSA) employing Hartree-Fock (HF) wave functions. Also the influence of core-polarization is examined. Our present results exhibit the existence of the minimum and the maximum in the CGOS curve, the Cooper minimum in the σ nl curves of Na and K, the important role of core-polarization and finally, the dependence of the VPSA CGOS on the incident energy.

  12. Alkali Metal Thermoelectric Conversion (AMTEC) for space nuclear power systems

    NASA Technical Reports Server (NTRS)

    Bankston, C. P.; Cole, T.; Khanna, S. K.; Thakoor, A. P.

    1985-01-01

    Performance parameters of the Alkali Metal Thermoelectric Converter (AMTEC) for a 100 kW electric power system have been calculated at four technological levels assuming a heat pipe-cooled nuclear reactor heat source. The most advanced level considered would operate between 1180 K converter temperature and 711 K radiator temperature at 16 percent efficiency, and would weigh 1850 kg with a radiator area of 43 sq m. In addition, electrode research studies for the AMTEC systems have been conducted utilizing an experimental test cell of Bankston et al. (1983) and Mo and several Mo-Ti electrodes. It was found that the Mo-Ti electrodes offered no improvement in lifetime characteristics over the pure Mo electrodes, however, oxygen treatment of a degraded Mo electrode restored its specific power output to 90 percent of its original specific power and maintained this level for 60 hr, thus offering a potential for lifetime stability.

  13. Cold collisions of alkali-metal atoms and chromium atoms

    NASA Astrophysics Data System (ADS)

    Jeung, G.-H.; Hagebaum-Reignier, D.; Jamieson, M. J.

    2010-12-01

    We present ab initio potentials for ground state lithium, sodium, potassium and rubidium atoms interacting with ground state chromium atoms via the 6Σ+ and 8Σ+ states of the corresponding dimers. Each potential is matched to the leading van der Waals dispersion energy -C6/R6 - C8/R8 and an exchange energy; we list the values of C6, C8 and the exchange fitting parameters. We present calculated values from quantal and semi-classical approximations for the s-wave scattering length and effective range and the p-wave scattering volume for collisions of each of the alkali-metal atoms lithium, sodium, potassium and rubidium with 52chromium atoms and comment on s-wave scattering by 53chromium atoms.

  14. 3718-F Alkali Metal Treatment and Storage Facility Closure Plan

    SciTech Connect

    1991-12-01

    Since 1987, Westinghouse Hanford Company has been a major contractor to the U.S. Department of Energy-Richland Operations Office and has served as co-operator of the 3718-F Alkali Metal Treatment and Storage Facility, the waste management unit addressed in this closure plan. The closure plan consists of a Part A Dangerous waste Permit Application and a RCRA Closure Plan. An explanation of the Part A Revision (Revision 1) submitted with this document is provided at the beginning of the Part A section. The closure plan consists of 9 chapters and 5 appendices. The chapters cover: introduction; facility description; process information; waste characteristics; groundwater; closure strategy and performance standards; closure activities; postclosure; and references.

  15. Relativistic optimized effective potential method-application to alkali metals.

    PubMed

    Ködderitzsch, D; Ebert, H; Akai, H; Engel, E

    2009-02-11

    We present a relativistic formulation of the optimized effective potential method (ROEP) and its implementation within the Korringa-Kohn-Rostoker multiple scattering formalism. The scheme is an all-electron approach, treating core and band states formally on the same footing. We use exact exchange (EXX) as an approximation to the exchange correlation functional. Numerical four-component wavefunctions for the description of core and valence electrons and the corresponding ingredients of the ROEP integral equation are employed. The exact exchange expression for the valence states is reformulated in terms of the electronic Green's function that in turn is evaluated by making use of multiple scattering formalism. We present and discuss the application of the formalism to non-magnetic alkali metals. PMID:21715911

  16. Surface free energy of alkali and transition metal nanoparticles

    NASA Astrophysics Data System (ADS)

    Aqra, Fathi; Ayyad, Ahmed

    2014-09-01

    This paper addresses an interesting issue on the surface free energy of metallic nanoparticles as compared to the bulk material. Starting from a previously reported equation, a theoretical model, that involves a specific term for calculating the cohesive energy of nanoparticle, is established in a view to describe the behavior of surface free energy of metallic nanoparticles (using different shapes of particle: sphere, cube and disc). The results indicate that the behavior of surface energy is very appropriate for spherical nanoparticle, and thus, it is the most realistic shape of a nanoparticle. The surface energy of copper, silver, gold, platinum, tungsten, molybdenum, tantalum, paladium and alkali metallic nanoparticles is only prominent in the nanoscale size, and it decreases with the decrease of nanoparticle size. Thus, the surface free energy plays a more important role in determining the properties of nanoparticles than in bulk materials. It differs from shape to another, and falls down as the number of atoms (nanoparticle size) decreases. In the case of spherical nanoparticles, the onset of the sharp decrease in surface energy is observed at about 110 atom. A decrease of 16% and 45% in surface energy is found by moving from bulk to 110 atom and from bulk to 5 atom, respectively. The predictions are consistent with the reported data.

  17. Silicate stabilization studies in propylene glycol

    SciTech Connect

    Schwartz, S.A.

    1999-08-01

    In most North American and many European coolant formulations, the corrosion inhibition of heat-rejecting aluminum surfaces is provided by alkali metal silicates. But, their tendency towards polymerization, leading to gelation and/or precipitation, can reduce the effectiveness of a coolant. This paper presents the results of experiments which illustrate formulation-dependent behavior of inorganic silicate in propylene glycol compositions. Specific examples of the effects of glycol matrix, stabilizer type, and hard water on silicate stabilization are provided.

  18. Compliant alkali silicate sealing glass for solid oxide fuel cell applications: Thermal cycle stability and chemical compatibility

    NASA Astrophysics Data System (ADS)

    Chou, Yeong-Shyung; Thomsen, E. C.; Williams, R. T.; Choi, J.-P.; Canfield, N. L.; Bonnett, J. F.; Stevenson, J. W.; Shyam, A.; Lara-Curzio, E.

    2011-03-01

    An alkali silicate glass (SCN-1) is currently being evaluated as a candidate sealing glass for solid oxide fuel cell (SOFC) applications. The glass containing ∼17 mole% alkalis (K2O and Na2O) remains vitreous and compliant during SOFC operation, unlike conventional SOFC sealing glasses, which experience substantial devitrification after the sealing process. The non-crystallizing compliant sealing glass has lower glass transition and softening temperatures since the microstructure remains glassy without significant crystallite formation, and hence can relieve or reduce residual stresses and also has the potential for crack healing. Sealing approaches based on compliant glass will also need to satisfy all the mechanical, thermal, chemical, physical, and electrical requirements for SOFC applications, not only in bulk properties but also at sealing interfaces. In this first of a series of papers we will report the thermal cycle stability of the glass when sealed between two SOFC components, i.e., a NiO/YSZ anode supported YSZ bilayer and a coated ferritic stainless steel interconnect material. High temperature leak rates were monitored versus thermal cycles between 700 and 850 °C using back pressures ranging from 1.4 to 6.8 kPa (0.2-1.0 psi). Isothermal stability was also evaluated in a dual environment consisting of flowing dilute H2 fuel versus ambient air. In addition, chemical compatibility at the alumina and YSZ interfaces was examined with scanning electron microscopy and energy dispersive spectroscopy. The results shed new light on the topic of SOFC glass seal development.

  19. 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. PMID:22525260

  20. On the structure of defect centers in γ-irradiated alkali silicate glasses

    NASA Astrophysics Data System (ADS)

    Cases, R.; Griscom, D. L.

    1984-02-01

    An EPR study after room temperature γ-irradiation on potassium silicate glasses of two chemical compositions and different 17O and 29Si isotopic enrichments has been carried out. Isochronal anneal experiments on 17O-enriched samples have confirmed the model for the trapped-hole center HC 1 as comprising a trapped hole on a pure 2p π orbital of a single nonbridging oxygen. Besides the well known HC 1 and HC 2 EPR spectra, new resonances have been isolated and identified as due to three types of oxygen-related defects (interstitial O 2- ions; O 2- bonded to the glass network; and interstitial ozonide ions O 3-). Using 29Si-enriched samp simulations a 370 G doublet has been demonstrated to arise from an E'-like defect for which a tentative model is given. The formation of all these defects by irradiation depends on chemical composition of the glass.

  1. (abstract) Alkali Metal Diffusion Through Porous Metal Electrodes in AMTEC Cells

    NASA Technical Reports Server (NTRS)

    Williams, R. M.; Jeffries-Nakamura, B.; Ryan, M. A.; Underwood, M. L.; O'Connor, D.; Kisor, A.; Kikkert, S.

    1993-01-01

    The mechanisms of mass transport of an alkali metal through porous metal electrodes in alkali metal thermal-to-electric converter AMTEC cells is important in optimizing these high current density devices, but also affords the opportunity to investigate a variety of simple mass transport modes at high temperatures via electrochemical techniques. We have previously reported evidence of ionic, free molecular flow, and surface transport of sodium in several types of AMTEC electrodes. Quantitative investigations of Na transport through WPt(sub 3.5) via surface or grain boundary diffusion, and K transport through porous Mo electrodes by free molecular flow, over large ranges of temperature have been performed. WPt(sub 3.5) has especially low transport impedance over the 950 to 1200K temperature range. New results are the Na through porous WPt(sub 3.5) and K through porous Mo diffusion rates and mechanisms.

  2. Method of treating alkali metal sulfide and carbonate mixtures

    DOEpatents

    Kohl, Arthur L.; Rennick, Robert D.; Savinsky, Martin W.

    1978-01-01

    A method of removing and preferably recovering sulfur values from an alkali metal sulfide and carbonate mixture comprising the steps of (1) introducing the mixture in an aqueous medium into a first carbonation zone and reacting the mixture with a gas containing a major amount of CO.sub.2 and a minor amount of H.sub.2 S; (2) introducing the resultant product from step 1 into a stripping zone maintained at subatmospheric pressure, and contacting this product with steam to produce a gaseous mixture, comprising H.sub.2 S and water vapor, and a liquor of reduced sulfide content; (3) introducing the liquor of reduced sulfide content into a second carbonation zone, and reacting the liquor with substantially pure gaseous CO.sub.2 in an amount sufficient to precipitate bicarbonate crystals and produce an offgas containing CO.sub.2 and H.sub.2 S for use in step 1; (4) recovering the bicarbonate crystals from step 3, and thermally decomposing the crystals to produce an alkaline metal carbonate product and a substantially pure CO.sub.2 offgas for use in step 3.

  3. 40 CFR 721.5985 - Fatty alkyl phosphate, alkali metal salt (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.5985 Fatty alkyl phosphate, alkali metal salt (generic). (a) Chemical... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Fatty alkyl phosphate, alkali...

  4. Field desorption microscopy of graphene on iridium in intercalation with alkali metals

    NASA Astrophysics Data System (ADS)

    Bernatskii, D. P.; Pavlov, V. G.

    2014-12-01

    Field-desorption and field-emission electron microscopy methods have been used to study the effect of a strong electric field on the processes of potassium and cesium desorption from the graphene surface on an iridium field emitter. It was found that two phases of field desorption may exist for these alkali metals. In the low-field phase, alkali metal atoms adsorbed on the surface are desorbed. The existence of the high-field phase is attributed to the egress from under the graphene film and ionization of intercalated alkali metal atoms under the action of the electric field.

  5. Calculation of radiative corrections to E1 matrix elements in the neutral alkali metals

    SciTech Connect

    Sapirstein, J.; Cheng, K.T.

    2005-02-01

    Radiative corrections to E1 matrix elements for ns-np transitions in the alkali-metal atoms lithium through francium are evaluated. They are found to be small for the lighter alkali metals but significantly larger for the heavier alkali metals, and in the case of cesium much larger than the experimental accuracy. The relation of the matrix element calculation to a recent decay rate calculation for hydrogenic ions is discussed, and application of the method to parity nonconservation in cesium is described.

  6. Metal/silicate fractionation in the solar system.

    NASA Technical Reports Server (NTRS)

    Lewis, J. S.

    1972-01-01

    Fractionation between the metal and silicate components of objects in the inner solar system has long been recognized as a necessity in order to explain the observed density variations of the terrestrial planets and the H-group, L-group dichotomy of the ordinary chondrites. This paper discusses the densities of the terrestrial planets in light of current physical and chemical models of processes in the solar nebula. It is shown that the observed density trends in the inner solar system need not be the result of special fractionation processes, and that the densities of the planets may be direct results of simultaneous application of both physical and chemical restraints on the structure of the nebula, most notably the variation of temperature with heliocentric distance. The density of Mercury is easily attributed to accretion at temperatures so high that MgSiO3 is only partially retained but Fe metal is condensed. The densities of the other terrestrial planet are shown to be due to different degrees of retention of S, O and H as FeS, FeO and hydrous silicates produced in chemical equilibrium between condensates and solar-composition gases.

  7. Nitrogen Partitioning Between Reduced Silicate Melts and Metallic Iron Alloys

    NASA Astrophysics Data System (ADS)

    Armstrong, L. S.; Falksen, E.; Von Der Handt, A.; Hirschmann, M. M.

    2014-12-01

    Solubility and partitioning of elements during early planetary history is critical in understanding element concentrations and distribution in the terrestrial planets. Nitrogen is the most depleted element in the bulk silicate Earth relative to CI chondrites [1], which may be explained by its high pressure behavior under reduced conditions relevant to planetary accretion and differentiation. Under oxidized conditions N dissolves in silicate melts as N2, but as fO2 decreases N-H species become the dominant form of dissolved N and the solubility increases [2-7]. DNmetal/melt (the N partition coefficient between metal and melt) is affected by pressure, fO2, fH2, and metal composition [3-5] but with less than 20 published experiments over a wide pressure range, these dependencies have been poorly constrained. Here we present new N-bearing experiments on graphite-saturated silicate melts in equilibrium with Fe-rich metallic melts. Experiments were performed at 1.2 GPa and 1400 ˚C in a piston cylinder apparatus, with N added as Si3N4, FexN, and urea [(NH2)2CO] to basaltic starting compositions. Glassy and metallic run products were gold coated and analyzed by EMPA. Detection limits and standard errors in N concentrations were improved (e.g. better than 1% for > 0.4 wt% N) relative to previous studies [2-5] by fitting non-linear backgrounds to wavelength-scans on standards and unknowns. Preliminary experiments with fO2 of IW-2 to IW-4 produced glasses with a maximum of 0.6 wt% N and metals with a maximum of 1.1 wt% N. DNmetal/melt are comparable to values at a similar pressure determined in the LH-DAC [5]. Further experiments will explore the effects of fO2 and H content on DN and N solubility. References: [1] Halliday (2013) GCA 105, 146-171. [2] Libourel et al. (2003) GCA 67, 4123-4135. [3] Kadik et al. (2011) Geochem. Int. 49, 429-438. [4] Kadik et al. (2013) PEPI 214, 14-24. [5] Roskosz et al. (2013) GCA 121, 15-28. [6] Stanley et al. (2014) GCA 129, 54-76. [7

  8. Method and composition for testing for the presence of an alkali metal

    DOEpatents

    Guon, Jerold

    1981-01-01

    A method and composition for detecting the presence of an alkali metal on the surface of a body such as a metal plate, tank, pipe or the like is provided. The method comprises contacting the surface with a thin film of a liquid composition comprising a light-colored pigment, an acid-base indicator, and a nonionic wetting agent dispersed in a liquid carrier comprising a minor amount of water and a major amount of an organic solvent selected from the group consisting of the lower aliphatic alcohols, ketones and ethers. Any alkali metal present on the surface in elemental form or as an alkali metal hydroxide or alkali metal carbonate will react with the acid-base indicator to produce a contrasting color change in the thin film, which is readily discernible by visual observation or automatic techniques.

  9. Zintl cluster chemistry in the alkali-metal-gallium systems

    SciTech Connect

    Henning, R.

    1998-03-27

    Previous research into the alkali-metal-gallium systems has revealed a large variety of networked gallium deltahedra. The clusters are analogues to borane clusters and follow the same electronic requirements of 2n+2 skeletal electrons for closo-deltahedra. This work has focused on compounds that do not follow the typical electron counting rules. The first isolated gallium cluster was found in Cs{sub 8}Ga{sub 11}. The geometry of the Ga{sub 11}{sup 7{minus}} unit is not deltahedral but can be described as a penta-capped trigonal prism. The reduction of the charge from a closo-Ga{sub 11}{sup 13{minus}} to Ga{sub 11}{sup 7{minus}} is believed to be the driving force of the distortion. The compound is paramagnetic because of an extra electron but incorporation of a halide atom into the structure captures the unpaired electron and forms a diamagnetic compound. A second isolated cluster has been found in Na{sub 10}Ga{sub 10}Ni where the tetra-capped trigonal prismatic gallium is centered by nickel. Stabilization of the cluster occurs through Ni-Ga bonding. A simple two-dimensional network occurs in the binary K{sub 2}Ga{sub 3} Octahedra are connected through four waist atoms to form a layered structure with the potassium atoms sitting between the layers. Na{sub 30.5}Ga{sub 60{minus}x}Ag{sub x} is nonstoichiometric and needs only a small amount of silver to form (x {approximately} 2--6). The structure is composed of three different clusters which are interconnected to form a three-dimensional structure. The RbGa{sub 3{minus}x}Au{sub x} system is also nonstoichiometric with a three-dimensional structure composed of Ga{sub 8} dodecahedra and four-bonded gallium atoms. Unlike Na{sub 30.5}Ga{sub 60{minus}x}Ag{sub x}, the RbGa{sub 3} binary is also stable. The binary is formally a Zintl phase but the ternary is not. Some chemistry in the alkali-metal-indium system also has been explored. A new potassium-indium binary is discussed but the structure has not been completely

  10. (abstract) Experimental and Modeling Studies of the Exchange Current at the Alkali Beta'-Alumina/Porous Electrode/Alkali Metal Vapor Three Phase Boundary

    NASA Technical Reports Server (NTRS)

    Williams, R. M.; Jeffries-Nakamura, B.; Ryan, M. A.; Underwood, M. L.; O'Connor, D.; Kikkert, S.

    1993-01-01

    The microscopic mechanism of the alkali ion-electron recombination reaction at the three phase boundary zone formed by a porous metal electrode in the alkali vapor on the surface of an alkali beta'-alumina solid electrolyte (BASE) ceramic has been studied by comparison of the expected rates for the three simplest reaction mechanisms with known temperature dependent rate data; and the physical parameters of typical porous metal electrode/BASE/alkali metal vapor reaction zones. The three simplest reactions are tunneling of electrons from the alkali coated electrode to a surface bound alkali metal ion; emission of an electron from the electrode with subsequent capture by a surface bound alkali metal ion; and thermal emission of an alkali cation from the BASE and its capture on the porous metal electrode surface where it may recombine with an electron. Only the first reaction adequately accounts for both the high observed rate and its temperature dependence. New results include crude modeling of simple, one step, three phase, solid/solid/gas electrochemical reaction.

  11. Modification of alkali metals on silicon-based nanoclusters: An enhanced nonlinear optical response

    NASA Astrophysics Data System (ADS)

    Li, Xiaojun; Han, Quan; Yang, Xiaohui; Song, Ruijuan; Song, Limei

    2016-08-01

    Structures, chemical stabilities and nonlinear optical properties of alkali metals-adsorbed niobium-doped silicon (M@SinNb+) clusters are investigated using the DFT methods. The alkali metals prefer energetically to be attached as bridged bond rather than M-Si single bond in most of optimized structures. Adsorption of alkali metals on doped silicon clusters gradually enhances their chemical stabilities with increasing cluster size. Noteworthily, the first hyperpolarizabilities (βtot) of the M@SinNb+ clusters, obtained by using the long-range corrected CAM-B3LYP functional, are large enough to establish their strong nonlinear optical behavior, especially for M@Si9Nb+ (M = Li, Na, and K), and the enhanced βtot ordering by alkali metals is Na > K > Li.

  12. Is Electronegativity a Useful Descriptor for the "Pseudo-Alkali-Metal" NH4?

    SciTech Connect

    Whiteside, Alexander; Xantheas, Sotiris S.; Gutowski, Maciej S.

    2011-11-18

    Molecular ions in the form of "pseudo-atoms" are common structural motifs in chemistry, with properties that are transferrable between different compounds. We have determined the electronegativity of the "pseudo-alkali metal" ammonium (NH4) and evaluated its reliability as a descriptor in comparison to the electronegativities of the alkali metals. The computed properties of its binary complexes with astatine and of selected borohydrides confirm the similarity of NH4 to the alkali metal atoms, although the electronegativity of NH4 is relatively large in comparison to its cationic radius. We paid particular attention to the molecular properties of ammonium (angular anisotropy, geometric relaxation, and reactivity), which can cause deviations from the behaviour expected of a conceptual "true alkali metal" with this electronegativity. These deviations allow for the discrimination of effects associated with the polyatomic nature of NH4.

  13. Is electronegativity a useful descriptor for the pseudo-alkali metal NH4?

    PubMed

    Whiteside, Alexander; Xantheas, Sotiris S; Gutowski, Maciej

    2011-11-18

    Molecular ions in the form of "pseudo-atoms" are common structural motifs in chemistry, with properties that are transferrable between different compounds. We have determined one such property--the electronegativity--for the "pseudo-alkali metal" ammonium (NH(4)), and evaluated its reliability as a descriptor versus the electronegativities of the alkali metals. The computed properties of ammonium's binary complexes with astatine and of selected borohydrides confirm the similarity of NH(4) to the alkali metal atoms, although the electronegativity of NH(4) is relatively large in comparison to its cationic radius. We have paid particular attention to the molecular properties of ammonium (angular anisotropy, geometric relaxation and reactivity), which can cause deviations from the behaviour expected of a conceptual "true alkali metal" with this electronegativity. These deviations allow for the discrimination of effects associated with the molecular nature of NH(4). PMID:21928287

  14. Accretion and core formation: constraints from metal-silicate partitioning.

    PubMed

    Wood, Bernard J

    2008-11-28

    Experimental metal-silicate partitioning data for Ni, Co, V, Cr, Nb, Mn, Si and W were used to investigate the geochemical consequences of a range of models for accretion and core formation on Earth. The starting assumptions were chondritic ratios of refractory elements in the Earth and the segregation of metal at the bottom of a magma ocean, which deepened as the planet grew and which had, at its base, a temperature close to the liquidus of the silicate. The models examined were as follows. (i) Continuous segregation from a mantle which is chemically homogeneous and which has a fixed oxidation state, corresponding to 6.26 per cent oxidized Fe. Although Ni, Co and W partitioning is consistent with chondritic ratios, the current V content of the silicate Earth cannot be reconciled with core segregation under these conditions of fixed oxidation state. (ii) Continuous segregation from a mantle which is chemically homogeneous but in which the Earth became more oxidized as it grew. In this case, the Ni, Co, W, V, Cr and Nb contents of core and mantle are easily matched to those calculated from the chondritic ratios of refractory elements. The magma ocean is calculated to maintain a thickness approximately 35 per cent of the depth to the core-mantle boundary in the accreting Earth, yielding a maximum pressure of 44GPa. This model yields a Si content of the core of 5.7 per cent, in good agreement with cosmochemical estimates and with recent isotopic data. (iii) Continuous segregation from a mantle which is not homogeneous and in which the core equilibrates with a restricted volume of mantle at the base of the magma ocean. This is found to increase depth of the magma ocean by approximately 50 per cent. All of the other elements (except Mn) have partitioning consistent with chondritic abundances in the Earth, provided the Earth became, as before, progressively oxidized during accretion. (iv) Continuous segregation of metal from a crystal-melt mush. In this case, pressures

  15. Design of low work function materials using alkali metal-doped transition metal dichalcogenides

    NASA Astrophysics Data System (ADS)

    Kim, Sol; Lee, Man Young; Lee, Seong; Jhi, Seung-Hoon

    Engineering the work function is a key issue in surface science. Particularly, discovering the materials that have work functions less than 1eV is essential for efficient thermionic energy conversion. The lowest work function of materials, reported so far, is in a range of about 1eV. To design low work function materials, we chose MX2 (M =Mo and W; X =S, Se and Te) as substrates and alkali metals (Li, Na, K, Rb and Cs) as dopants, and studied their electronic structures, charge transfer, induced surface dipole moment, and work function using first-principles calculations. We found that the charge transfer from alkali metals to MX2 substrates decreases as the atomic radius of alkali metals increases. Regardless of the amount of the charge transfer, K on WTe2 exhibits the biggest surface dipole moment, which consequently makes the surface work function the lowest. Also, we found a correlation between the binding distance and the work function.

  16. In situ formation of coal gasification catalysts from low cost alkali metal salts

    DOEpatents

    Wood, Bernard J.; Brittain, Robert D.; Sancier, Kenneth M.

    1985-01-01

    A carbonaceous material, such as crushed coal, is admixed or impregnated with an inexpensive alkali metal compound, such as sodium chloride, and then pretreated with a stream containing steam at a temperature of 350.degree. to 650.degree. C. to enhance the catalytic activity of the mixture in a subsequent gasification of the mixture. The treatment may result in the transformation of the alkali metal compound into another, more catalytically active, form.

  17. The effect of different alkali metal hydroxides on nickel electrode life

    NASA Technical Reports Server (NTRS)

    Lim, H. S.; Verzwyvelt, S. A.; Clement, S. K.

    1988-01-01

    An accelerated cycle-life test (100-percent depth of discharge) of a sintered-type Ni electrode has been carried out in a flooded cell containing different alkali metal hydroxide electrolytes such as LiOH, NaOH, KOH, RbOH, and CsOH. Decrease in Ni electrode capacity with cycling was reduced as the radius of the alkali metal ions, with possible exception of CsOH.

  18. 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.

  19. Hydrogen-alkali exchange between silicate melts and two-phase aqueous mixtures: an experimental investigation

    NASA Astrophysics Data System (ADS)

    Williams, Thomas J.; Candela, Philip A.; Piccoli, Philip M.

    Experiments were performed in the three-phase system high-silica rhyolite melt + low-salinity aqueous vapor + hydrosaline brine, to investigate the exchange equilibria for hydrogen, potassium, and sodium in magmatic-hydrothermal systems at 800 °C and 100 MPa, and 850 °C and 50 MPa. The Kaqm/meltH,Na and Kaqm/meltH,K for hydrogen-sodium exchange between a vapor + brine mixture and a silicate melt are inversely proportional to the total chloride concentration (ΣCl) in the vapor + brine mixture indicating that HCl/NaCl and HCl/KCl are higher in the low-salinity aqueous vapor relative to high-salinity brine. The equilibrium constants for vapor/melt and brine/melt exchange were extracted from regressions of Kaqm/meltH,Na and Kaqm/meltH,K versus the proportion of aqueous vapor relative to brine in the aqueous mixture (Faqv) at P and T, expressed as a function of ΣCl. No significant pressure effect on the empirically determined exchange constants was observed for the range of pressures investigated. Model equilibrium constants are: Kaqv/meltH,Na(vapor/melt)=26(+/-1.3) at 100 MPa (800 °C), and 19( +/- 7.0) at 50 MPa (850 °C) Kaqv/meltH,K=14(+/-1.1) at 100 MPa (800 °C), and 24(+/-12) at 50 MPa (850 °C) Kaqb/meltH,b(brine/melt)= 1.6(+/-0.7) at 100 MPa (800 °C), and 3.9(+/-2.3) at 50 MPa (850 °C) and Kaqb/meltH,K=2.7(+/-1.2) at 100 MPa (800 °C) and 3.8(+/-2.3) at 50 MPa (850 °C). Values for Kaqv/meltH,K and Kaqb/meltH,K were used to calculate KCl/HCl in the aqueous vapor and brine as a function of melt aluminum saturation index (ASI: molar Al2O3/(K2O+Na2O+CaO) and pressure. The model log KCl/HCl values show that a change in melt ASI from peraluminous (ASI = 1.04) to moderately metaluminous (ASI = 1.01) shifts the cooling pathway (in temperature-log KCl/HCl space) of the aqueous vapor toward the andalusite+muscovite+K-feldspar reaction point.

  20. Alkali Metal Variation and Twisting of the FeNNFe Core in Bridging Diiron Dinitrogen Complexes.

    PubMed

    McWilliams, Sean F; Rodgers, Kenton R; Lukat-Rodgers, Gudrun; Mercado, Brandon Q; Grubel, Katarzyna; Holland, Patrick L

    2016-03-21

    Alkali metal cations can interact with Fe-N2 complexes, potentially enhancing back-bonding or influencing the geometry of the iron atom. These influences are relevant to large-scale N2 reduction by iron, such as in the FeMoco of nitrogenase and the alkali-promoted Haber-Bosch process. However, to our knowledge there have been no systematic studies of a large range of alkali metals regarding their influence on transition metal-dinitrogen complexes. In this work, we varied the alkali metal in [alkali cation]2[LFeNNFeL] complexes (L = bulky β-diketiminate ligand) through the size range from Na(+) to K(+), Rb(+), and Cs(+). The FeNNFe cores have similar Fe-N and N-N distances and N-N stretching frequencies despite the drastic change in alkali metal cation size. The two diketiminates twist relative to one another, with larger dihedral angles accommodating the larger cations. In order to explain why the twisting has so little influence on the core, we performed density functional theory calculations on a simplified LFeNNFeL model, which show that the two metals surprisingly do not compete for back-bonding to the same π* orbital of N2, even when the ligand planes are parallel. This diiron system can tolerate distortion of the ligand planes through compensating orbital energy changes, and thus, a range of ligand orientations can give very similar energies. PMID:26925968

  1. Removal of oxides from alkali metal melts by reductive titration to electrical resistance-change end points

    DOEpatents

    Tsang, Floris Y.

    1980-01-01

    Alkali metal oxides dissolved in alkali metal melts are reduced with soluble metals which are converted to insoluble oxides. The end points of the reduction is detected as an increase in electrical resistance across an alkali metal ion-conductive membrane interposed between the oxide-containing melt and a material capable of accepting the alkali metal ions from the membrane when a difference in electrical potential, of the appropriate polarity, is established across it. The resistance increase results from blocking of the membrane face by ions of the excess reductant metal, to which the membrane is essentially non-conductive.

  2. Half metallic ferromagnetism in alkali metal nitrides MN (M = Rb, Cs): A first principles study

    SciTech Connect

    Murugan, A. Rajeswarapalanichamy, R. Santhosh, M. Sudhapriyanga, G.; Kanagaprabha, S.

    2014-04-24

    The structural, electronic and elastic properties of two alkali metal nitrides (MN: M= Rb, Cs) are investigated by the first principles calculations based on density functional theory using the Vienna ab-initio simulation package. At ambient pressure the two nitrides are stable in ferromagnetic state with CsCl structure. The calculated lattice parameters are in good agreement with the available results. The electronic structure reveals that these materials are half metallic in nature. A pressure-induced structural phase transition from CsCl to ZB phase is observed in RbN and CsN.

  3. Method for inhibiting alkali metal corrosion of nickel-containing alloys

    DOEpatents

    DeVan, Jackson H.; Selle, James E.

    1983-01-01

    Structural components of nickel-containing alloys within molten alkali metal systems are protected against corrosion during the course of service by dissolving therein sufficient aluminum, silicon, or manganese to cause the formation and maintenance of a corrosion-resistant intermetallic reaction layer created by the interaction of the molten metal, selected metal, and alloy.

  4. Note: An ion source for alkali metal implantation beneath graphene and hexagonal boron nitride monolayers on transition metals

    NASA Astrophysics Data System (ADS)

    de Lima, L. H.; Cun, H. Y.; Hemmi, A.; Kälin, T.; Greber, T.

    2013-12-01

    The construction of an alkali-metal ion source is presented. It allows the acceleration of rubidium ions to an energy that enables the penetration through monolayers of graphene and hexagonal boron nitride. Rb atoms are sublimated from an alkali-metal dispenser. The ionization is obtained by surface ionization and desorption from a hot high work function surface. The ion current is easily controlled by the temperature of ionizer. Scanning Tunneling Microscopy measurements confirm ion implantation.

  5. Note: An ion source for alkali metal implantation beneath graphene and hexagonal boron nitride monolayers on transition metals

    SciTech Connect

    Lima, L. H. de; Cun, H. Y.; Hemmi, A.; Kälin, T.; Greber, T.

    2013-12-15

    The construction of an alkali-metal ion source is presented. It allows the acceleration of rubidium ions to an energy that enables the penetration through monolayers of graphene and hexagonal boron nitride. Rb atoms are sublimated from an alkali-metal dispenser. The ionization is obtained by surface ionization and desorption from a hot high work function surface. The ion current is easily controlled by the temperature of ionizer. Scanning Tunneling Microscopy measurements confirm ion implantation.

  6. Bounds on metal-silicate equilibration conditions during core formation

    NASA Astrophysics Data System (ADS)

    Deguen, Renaud

    2016-04-01

    Much of the Earth was built by high-energy impacts of planetesimals and embryos, many of these impactors already differentiated, with metallic cores of their own. Geochemical data provide critical information on the timing of accretion and the prevailing physical conditions. The comparison between the inferred core/mantle partitioning with the experimentally determined partitioning behavior of a number of siderophile elements can be used to place constraints on the conditions (pressure, temperature, oxygen fugacity) under which the metal and silicates equilibrated before separating to form the core and mantle. The main limitation of this approach is that the interpretation of the geochemical data in terms of equilibration conditions is non-unique. This is an ill-posed inverse problem, and the inversion is usually carried out by making a number of assumptions to close the problem and make it (artificially) well-posed. Here, we take another approach and derive exact bounds on the distribution of conditions of equilibration during Earth's formation and core mantle differentiation.

  7. Multi-photon processes in alkali metal vapors

    NASA Astrophysics Data System (ADS)

    Gai, Baodong; Hu, Shu; Li, Hui; Shi, Zhe; Cai, Xianglong; Guo, Jingwei; Tan, Yannan; Liu, Wanfa; Jin, Yuqi; Sang, Fengting

    2015-02-01

    Achieving population inversion through multi-photon cascade pumping is almost always difficult, and most laser medium work under 1-photon excitation mechanism. But for alkali atoms such as cesium, relatively large absorption cross sections of several low, cascading energy levels enable them properties such as up conversion. Here we carried out research on two-photon excitation alkali fluorescence. Two photons of near infrared region are used to excite alkali atoms to n 2 D5/2, n 2 D3/2 or higher energy levels, then the blue fluorescence of (n+1) 2 P3/2,(n+1) 2 P1/2-->n 2 S1/2 are observed. Different pumping paths are tried and by the recorded spectra, transition routes of cesium are deducted and concluded. Finally the possibility of two-photon style DPALs (diode pumped alkali laser) are discussed, such alkali lasers can give output wavelengths in the shorter end of visual spectroscopy (400-460 nm) and are expected to get application in underwater communication and material laser processing.

  8. Metal-silicate partitioning of Ni and Co in a deep magma ocean

    NASA Astrophysics Data System (ADS)

    Siebert, Julien; Badro, James; Antonangeli, Daniele; Ryerson, Frederick J.

    2012-03-01

    The pattern of siderophile (iron-loving) element abundance in the silicate portion of the Earth is a consequence of metal separation during core formation. The apparent excess of nickel and cobalt in mantle-derived rocks has been attributed to metal-silicate equilibration in a deep terrestrial magma ocean. Based on the extrapolation of phase equilibria and metal-silicate partitioning results obtained at lower pressure (P) and temperature (T), previous estimates of the P-T of equilibration are all greater than 25 GPa and 3000 K. Using the laser-heated diamond anvil cell, we have extended metal-silicate partitioning measurements for Ni and Co to 75 GPa and 4400 K, exceeding the liquidus temperatures for both metal and silicate (basalt or peridotite) and, therefore, achieving thermodynamic conditions directly comparable to those of the magma ocean. The metal-silicate partition coefficients of nickel and cobalt decrease with increasing pressure and reach the values required to yield present mantle concentrations at ~ 50 GPa. At these conditions, silicon and oxygen concentrations measured in the metallic liquid allow to solve the seismically constrained core density deficit. Above 60 GPa, the partition coefficients become too low, resulting in an overabundance of Ni and Co in the silicate mantle. Our data therefore support the paradigm of core formation in a deep mama ocean, providing an upper bound for the depth at which Earth's core may have formed, and explaining the main geophysical (density) and geochemical (excess siderophile elements) observables.

  9. Experimental determination of the Si isotope fractionation factor between liquid metal and liquid silicate

    NASA Astrophysics Data System (ADS)

    Hin, Remco C.; Fitoussi, Caroline; Schmidt, Max W.; Bourdon, Bernard

    2014-02-01

    The conditions of core formation and the abundances of the light elements in Earth's core remain debated. Silicon isotope fractionation provides a tool contributing to this subject. We present experimentally determined Si isotope fractionation factors between liquid metal and liquid silicate at 1450 °C and 1750 °C, which allow calibrating the temperature dependence of Si isotope fractionation. Experiments were performed in a centrifuging piston cylinder at 1 GPa, employing both graphite and MgO capsules. Tin was used to lower the melting temperature of the metal alloys for experiments performed at 1450 °C. Tests reveal that neither Sn nor C significantly affects Si isotope fractionation. An alkaline fusion technique was employed to dissolve silicate as well as metal phases prior to ion exchange chemistry and mass spectrometric analysis. The results show that metal is consistently enriched in light isotopes relative to the silicate, yielding average metal-silicate fractionation factors of -1.48±0.08‰ and -1.11±0.14‰ at 1450 °C and 1750 °C, respectively. The temperature dependence of equilibrium Si isotope fractionation between metal and silicate can thus be described as Δ30SiMetal-Silicate=-4.42(±0.05)×106/T2. The Si isotope equilibrium fractionation is thus about 1.7 times smaller than previously proposed on the basis of experiments. A consequence of this smaller fractionation is that the calculated difference between the Si isotope composition of the bulk Earth and that of the bulk silicate Earth generated by core formation is smaller than previously thought. It is therefore increasingly difficult to match the Si isotope composition of the bulk silicate Earth with that of chondrites for metal-silicate equilibration temperatures above ∼2500 K. This suggests that Si isotopes were more sensitive to the early stages of core formation when low oxygen fugacities allowed significant incorporation of Si into metal.

  10. Progress in High-Field Optical Pumping of Alkali Metal Nuclei

    NASA Astrophysics Data System (ADS)

    Patton, B.; Ishikawa, K.; Jau, Y.-Y.; Happer, W.

    2006-05-01

    We present preliminary results of an attempt to polarize alkali metal nuclei via optical pumping in a large (9.4-tesla) magnetic field. NMR measurements of ^87Rb and ^133Cs films in optical cells will be reported. Depopulation pumping of alkalis can easily produce electron polarizations of order unity, as measured during spin-exchange optical pumping of noble gases [1]. At low magnetic fields (< ˜1 kG), the strong hyperfine coupling between the alkali electron and nucleus allows angular momentum exchange from one to the other, resulting in nuclear polarization enhancement through optical pumping. In the high magnetic fields required for NMR, however, this interaction is largely decoupled and electron-nuclear spin exchange must rely upon the δA I .S interaction induced by buffer gas collisions (also called the ``Carver rate''). High-field optical pumping experiments may allow for a more precise measurement of this rate, as well as yielding insight into the transfer of angular momentum from the polarized alkali vapor to the bulk alkali metal on the cell walls. The technical challenges of high-resolution NMR of alkali metals at 9.4 tesla will be discussed. 1. E. Babcock, I. Nelson, S. Kadlecek, et al., Physical Review Letters 91, 123003 (2003).

  11. Alkali Metal Backup Cooling for Stirling Systems - Experimental Results

    NASA Technical Reports Server (NTRS)

    Schwendeman, Carl; Tarau, Calin; Anderson, William G.; Cornell, Peggy A.

    2013-01-01

    In a Stirling Radioisotope Power System (RPS), heat must be continuously removed from the General Purpose Heat Source (GPHS) modules to maintain the modules and surrounding insulation at acceptable temperatures. The Stirling convertor normally provides this cooling. If the Stirling convertor stops in the current system, the insulation is designed to spoil, preventing damage to the GPHS at the cost of an early termination of the mission. An alkali-metal Variable Conductance Heat Pipe (VCHP) can be used to passively allow multiple stops and restarts of the Stirling convertor. In a previous NASA SBIR Program, Advanced Cooling Technologies, Inc. (ACT) developed a series of sodium VCHPs as backup cooling systems for Stirling RPS. The operation of these VCHPs was demonstrated using Stirling heater head simulators and GPHS simulators. In the most recent effort, a sodium VCHP with a stainless steel envelope was designed, fabricated and tested at NASA Glenn Research Center (GRC) with a Stirling convertor for two concepts; one for the Advanced Stirling Radioisotope Generator (ASRG) back up cooling system and one for the Long-lived Venus Lander thermal management system. The VCHP is designed to activate and remove heat from the stopped convertor at a 19 C temperature increase from the nominal vapor temperature. The 19 C temperature increase from nominal is low enough to avoid risking standard ASRG operation and spoiling of the Multi-Layer Insulation (MLI). In addition, the same backup cooling system can be applied to the Stirling convertor used for the refrigeration system of the Long-lived Venus Lander. The VCHP will allow the refrigeration system to: 1) rest during transit at a lower temperature than nominal; 2) pre-cool the modules to an even lower temperature before the entry in Venus atmosphere; 3) work at nominal temperature on Venus surface; 4) briefly stop multiple times on the Venus surface to allow scientific measurements. This paper presents the experimental

  12. Alkali Metal Backup Cooling for Stirling Systems - Experimental Results

    NASA Technical Reports Server (NTRS)

    Schwendeman, Carl; Tarau, Calin; Anderson, William G.; Cornell, Peggy A.

    2013-01-01

    In a Stirling Radioisotope Power System (RPS), heat must be continuously removed from the General Purpose Heat Source (GPHS) modules to maintain the modules and surrounding insulation at acceptable temperatures. The Stirling convertor normally provides this cooling. If the Stirling convertor stops in the current system, the insulation is designed to spoil, preventing damage to the GPHS at the cost of an early termination of the mission. An alkali-metal Variable Conductance Heat Pipe (VCHP) can be used to passively allow multiple stops and restarts of the Stirling convertor. In a previous NASA SBIR Program, Advanced Cooling Technologies, Inc. (ACT) developed a series of sodium VCHPs as backup cooling systems for Stirling RPS. The operation of these VCHPs was demonstrated using Stirling heater head simulators and GPHS simulators. In the most recent effort, a sodium VCHP with a stainless steel envelope was designed, fabricated and tested at NASA Glenn Research Center (GRC) with a Stirling convertor for two concepts; one for the Advanced Stirling Radioisotope Generator (ASRG) back up cooling system and one for the Long-lived Venus Lander thermal management system. The VCHP is designed to activate and remove heat from the stopped convertor at a 19 degC temperature increase from the nominal vapor temperature. The 19 degC temperature increase from nominal is low enough to avoid risking standard ASRG operation and spoiling of the Multi-Layer Insulation (MLI). In addition, the same backup cooling system can be applied to the Stirling convertor used for the refrigeration system of the Long-lived Venus Lander. The VCHP will allow the refrigeration system to: 1) rest during transit at a lower temperature than nominal; 2) pre-cool the modules to an even lower temperature before the entry in Venus atmosphere; 3) work at nominal temperature on Venus surface; 4) briefly stop multiple times on the Venus surface to allow scientific measurements. This paper presents the experimental

  13. Charge oscillations and structure for alkali-metal-doped polyacetylene

    NASA Astrophysics Data System (ADS)

    Baughman, R. H.; Murthy, N. S.; Eckhardt, H.; Kertesz, M.

    1992-11-01

    predictions for oligomers, and good agreement is obtained between calculated and observed x-ray photoelectron spectra for sodium-doped polyacetylene. Emphasis is placed on the results of crystallographic studies of alkali-metal-doped polyacetylene and on the relationship between the experimentally derived symmetry breaking in interchain packing and the molecular symmetry breaking predicted by theory. Since presently available experimental data are insufficient for complete determination of structure, the present theoretical results can be useful for refinements in the interpretation of these data, as well as for refined crystal-packing calculations.

  14. Fluorescent probes and bioimaging: alkali metals, alkaline earth metals and pH.

    PubMed

    Yin, Jun; Hu, Ying; Yoon, Juyoung

    2015-07-21

    All living species and life forms have an absolute requirement for bio-functional metals and acid-base equilibrium chemistry owing to the critical roles they play in biological processes. Hence, a great need exists for efficient methods to detect and monitor biometals and acids. In the last few years, great attention has been paid to the development of organic molecule based fluorescent chemosensors. The availability of new synthetic fluorescent probes has made fluorescence microscopy an indispensable tool for tracing biologically important molecules and in the area of clinical diagnostics. This review highlights the recent advances that have been made in the design and bioimaging applications of fluorescent probes for alkali metals and alkaline earth metal cations, including lithium, sodium and potassium, magnesium and calcium, and for pH determination within biological systems. PMID:25317749

  15. Dissolution Process of Palladium in Hydrochloric Acid: A Route via Alkali Metal Palladates

    NASA Astrophysics Data System (ADS)

    Kasuya, Ryo; Miki, Takeshi; Morikawa, Hisashi; Tai, Yutaka

    2015-12-01

    To improve the safety of the Pd recovery processes that use toxic oxidizers, dissolution of Pd in hydrochloric acid with alkali metal palladates was investigated. Alkali metal palladates were prepared by calcining a mixture of Pd black and alkali metal (Li, Na, and K) carbonates in air. Almost the entire amount of Pd was converted into Li2PdO2 after calcination at 1073 K (800 °C) using Li2CO3. In contrast, PdO was obtained by calcination at 1073 K (800 °C) using Na and K carbonates. Our results indicated that Li2CO3 is the most active reagent among the examined alkali metal carbonates for the formation of palladates. In addition, dissolution of the resulting Li2PdO2 in HCl solutions was evaluated under various conditions. In particular, Li2PdO2 rapidly dissolved in diluted (0.1 M) HCl at ambient temperature. Solubility of Pd of Li2PdO2 was found to be 99 pct or larger after dissolution treatment at 353 K (80 °C) for 5 minutes; in contrast, PdO hardly dissolved in 0.1 M HCl. The dissolution mechanism of Li2PdO2 in HCl was also elucidated by analysis of crystal structures and particulate properties. Since our process is completely free from toxic oxidizers, the dissolution process via alkali metal palladates is much safer than currently employed methods.

  16. Saturated vapor pressure above the amalgam of alkali metals in discharge lamps

    NASA Astrophysics Data System (ADS)

    Gavrish, S. V.

    2011-12-01

    A theoretical and numerical analysis of the evaporation process of two-component compounds in vapors of alkali metals in discharge lamps is presented. Based on the developed mathematical model of calculation of saturated vapor pressure of the metal above the amalgam, dependences of mass fractions of the components in the discharge volume on design parameters and thermophysical characteristics of the lamp are obtained.

  17. 40 CFR 721.10098 - Disubstituted benzoic acid, alkali metal salt (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... metal salt (generic). 721.10098 Section 721.10098 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10098 Disubstituted benzoic acid, alkali metal...

  18. 40 CFR 721.4663 - Fluorinated carboxylic acid alkali metal salts.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... metal salts. 721.4663 Section 721.4663 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.4663 Fluorinated carboxylic acid alkali metal salts. (a)...

  19. Carbon solution and partitioning between metallic and silicate melts in a shallow magma ocean: Implications for the origin and distribution of terrestrial carbon

    NASA Astrophysics Data System (ADS)

    Dasgupta, Rajdeep; Chi, Han; Shimizu, Nobumichi; Buono, Antonio S.; Walker, David

    2013-02-01

    The origin of bulk silicate Earth carbon inventory is unknown and the fate of carbon during the early Earth differentiation and core formation is a missing link in the evolution of the terrestrial carbon cycle. Here we present high pressure (P)-temperature (T) experiments that offer new constraints upon the partitioning of carbon between metallic and silicate melt in a shallow magma ocean. Experiments were performed at 1-5 GPa, 1600-2100 °C on mixtures of synthetic or natural silicates (tholeiitic basalt/alkali basalt/komatiite/fertile peridotite) and Fe-Ni-C ± Co ± S contained in graphite or MgO capsules. All the experiments produced immiscible Fe-rich metallic and silicate melts at oxygen fugacity (fO2) between ˜IW-1.5 and IW-1.9. Carbon and hydrogen concentrations of basaltic glasses and non-glassy quenched silicate melts were determined using secondary ionization mass spectrometry (SIMS) and speciation of dissolved C-O-H volatiles in silicate glasses was studied using Raman spectroscopy. Carbon contents of metallic melts were determined using both electron microprobe and SIMS. Our experiments indicate that at core-forming, reduced conditions, carbon in deep mafic-ultramafic magmas may dissolve primarily as various hydrogenated species but the total carbon storage capacity, although is significantly higher than solubility of CO2 under similar conditions, remains low (<500 ppm). The total carbon content in our reduced melts at graphite saturation increases with increasing melt depolymerization (NBO/T), consistent with recent spectroscopic studies, and modestly with increasing hydration. Carbon behaves as a metal-loving element during core-mantle separation and our experimental DCmetal/silicate varies between ˜4750 and ⩾150 and increases with increasing pressure and decreases with increasing temperature and melt NBO/T. Our data suggest that if only a trace amount of carbon (˜730 ppm C) was available during early Earth differentiation, most of it was

  20. Metal-Silicate Interactions at High Pressure and Temperature

    NASA Astrophysics Data System (ADS)

    Bouhifd, M.; Jephcoat, A.; Gautron, L.; Malavergne, V.; Catillon, G.

    2001-12-01

    Laser-heated diamond-anvil cell (LHDAC) experiments were carried out to determine the partition coefficients of Ni and Co between iron metal and several silicates. One challenge of these experiments is to analyze accurately small samples from the LHDAC with sub-micrometer spatial resolution. We used diamond anvils with 500 microns culets, and stainless-steel gaskets preindented to a thickness of 40μ m and drilled to a diameter of 200μ m. We used both compacted powders with several silicate glass compositions (ranging from SiO2 to basaltic composition simulating that of model C1 chondrite) and a 25μ m thick Fe-Ni-Co alloy foil. Thermal insulation from the diamonds was achieved by 10μ m-thick pure Al2O3 and solid argon pressure medium. Pressures were measured at room temperature before and after laser heating, with the ruby-fluorescence method. The samples were heated by a multimode YAG laser for an average of 10-15 minutes. Temperatures were determined spectro-radiometrically with a fit to a grey-body Planck function. Samples recovered after the runs were polished down to the heated surface and analyzed by electron microprobe (the electron beam is less than 1μ m and the resolution is about 1μ m), or characterized by Transmission Electron Microscopy (TEM). In addition, we have analyzed our samples using secondary ion mass spectrometry (SIMS) analysis. A successful overlap of results of these different analysis techniques will substantially increase confidence in the extension of experiments to lower-mantle conditions. Our preliminary results in the system Si-Al-Fe-Mg-Ca-Ni-Co-O, show a good agreement with those of multianvil experiments at low pressures (5-12 GPa) [1], and with increasing pressure until 50 GPa we observe the expected decrease of the partition coefficients of Ni and Co for the same redox conditions. The partition coefficients determined in our work at high pressures (5-50 GPa) and constant temperature (2500 +/- 200 K), DM = XMmetal

  1. Structural and Magnetic Diversity in Alkali-Metal Manganate Chemistry: Evaluating Donor and Alkali-Metal Effects in Co-complexation Processes.

    PubMed

    Uzelac, Marina; Borilovic, Ivana; Amores, Marco; Cadenbach, Thomas; Kennedy, Alan R; Aromí, Guillem; Hevia, Eva

    2016-03-24

    By exploring co-complexation reactions between the manganese alkyl Mn(CH2SiMe3)2 and the heavier alkali-metal alkyls M(CH2SiMe3) (M=Na, K) in a benzene/hexane solvent mixture and in some cases adding Lewis donors (bidentate TMEDA, 1,4-dioxane, and 1,4-diazabicyclo[2,2,2] octane (DABCO)) has produced a new family of alkali-metal tris(alkyl) manganates. The influences that the alkali metal and the donor solvent impose on the structures and magnetic properties of these ates have been assessed by a combination of X-ray, SQUID magnetization measurements, and EPR spectroscopy. These studies uncover a diverse structural chemistry ranging from discrete monomers [(TMEDA)2 MMn(CH2SiMe3)3] (M=Na, 3; M=K, 4) to dimers [{KMn(CH2SiMe3)3 ⋅C6 H6}2] (2) and [{NaMn(CH2SiMe3)3}2 (dioxane)7] (5); and to more complex supramolecular networks [{NaMn(CH2SiMe3)3}∞] (1) and [{Na2Mn2 (CH2SiMe3)6 (DABCO)2}∞] (7)). Interestingly, the identity of the alkali metal exerts a significant effect in the reactions of 1 and 2 with 1,4-dioxane, as 1 produces coordination adduct 5, while 2 forms heteroleptic [{(dioxane)6K2Mn2 (CH2SiMe3)4(O(CH2)2OCH=CH2)2}∞] (6) containing two alkoxide-vinyl anions resulting from α-metalation and ring opening of dioxane. Compounds 6 and 7, containing two spin carriers, exhibit antiferromagnetic coupling of their S=5/2 moments with varying intensity depending on the nature of the exchange pathways. PMID:26916525

  2. Electronic and nuclear dynamics in the frustrated photodesorption of alkali atoms from metals

    NASA Astrophysics Data System (ADS)

    Petek, Hrvoje

    2001-03-01

    Electronic and nuclear dynamics of alkali atom covered noble metal surfaces are investigated by the interferometric time-resolved two-photon photoemission technique [1]. Photoinduced charge transfer turns on the repulsive Coulomb force between the alkali atom and the metal surface thereby initiating the expulsion of alkali atoms from the surface. The resulting nuclear motion of alkali atoms is detected through changes in the surface electronic structure. In the extreme case of Cs/Cu(111), the alkali atom motion can be observed for up to 200 fs, which according to a Newton’s law model corresponds to the stretching of the Cu-Cs bond by 0.3 Å [2]. However, wave packet spreading due to the recoil-induced phonon generation retards the desorption process. Systematic dependence of the alkali atom lifetime on the crystal face, the substrate material, and the adsorbate polarizability provides insights into factors that stabilize adsorbates with respect to decay via the resonant charge transfer and inelastic electron-electron scattering [3]. 1 S. Ogawa, H. Nagano, and H. Petek, Phys. Rev. Lett. 82, 1931 (1999). 2 H. Petek, H. Nagano, M. J. Weida, and S. Ogawa, Science 288, 1402 (2000). 3 J. P. Gauyacq et al., Faraday Discuss. Chem. Soc. 117 (2000).

  3. Ternary Amides Containing Transition Metals for Hydrogen Storage: A Case Study with Alkali Metal Amidozincates.

    PubMed

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

    2015-11-01

    The alkali metal amidozincates Li4 [Zn(NH2)4](NH2)2 and K2[Zn(NH2)4] were, to the best of our knowledge, studied for the first time as hydrogen storage media. Compared with the LiNH2-2 LiH system, both Li4 [Zn(NH2)4](NH2)2-12 LiH and K2[Zn(NH2)4]-8 LiH systems showed improved rehydrogenation performance, especially K2[Zn(NH2)4]-8 LiH, which can be fully hydrogenated within 30 s at approximately 230 °C. The absorption properties are stable upon cycling. This work shows that ternary amides containing transition metals have great potential as hydrogen storage materials. PMID:26463124

  4. Metal-Silicate Differentiation from a Metal Pond Emulsion during Core Formation

    NASA Astrophysics Data System (ADS)

    Fleck, J.; Weeraratne, D. S.

    2011-12-01

    The terrestrial planets demonstrate a heavy bombardment of impacts in their early formation history. Impacts are violent, energetic collisions that may melt the surface and/or cause segregation of impactor material including silicates and liquid metal iron. Although theoretical studies have been done with conceptual models for metal diapir descent to form terrestrial planetary cores, physical or computer modeling studies are scarce due to the strong variations in physical properties between liquid metals and solid silicates. We use laboratory fluid experiments to study core formation processes using liquid metal gallium and high viscosity glucose syrup which provide the buoyancy ratios expected for planetary interiors and low Reynolds number flow dynamics. Preliminary results indicate that the physical process of sinking metal diapirs form trailing conduits that may drag low density surface magmatic material to the base of the mantle. The low density material collects, grows at the base of the box, and rises back to the surface. We compare two cases of a pond made of 1) liquid metal emulsion and 2) a smooth coalesced metal pond. We find that emulsion experiments entrain greater amounts of low density fluid to the base of the box. Once the metal diapir reaches the base, conduit material exhibits flow reversal to return buoyantly to the surface. In the case of coalesced liquid metal diapirs, low density conduit material returns to the surface through the pre-established conduit. In the emulsion diapir case, we observe the formation of a new thermo-chemical buoyant plume that grows, exits the conduit, and travels along a new pathway to the surface. Metal plume descent and chemical plume rise velocities are consistent with Stokes velocity. Estimates of metal-silicate plume sinking time and thermo-chemical plume rise time for terrestrial planetary interiors are provided. We suggest the observation of a thermo-chemical plume as a source for orogeny at the surface of

  5. Adsorption of alkali, alkaline-earth, and 3d transition metal atoms on silicene

    NASA Astrophysics Data System (ADS)

    Sahin, H.; Peeters, F. M.

    2013-02-01

    The adsorption characteristics of alkali, alkaline-earth, and transition metal adatoms on silicene, a graphene-like monolayer structure of silicon are analyzed by means of first-principles calculations. In contrast to graphene, interaction between the metal atoms and the silicene surface is quite strong due to its highly reactive buckled hexagonal structure. In addition to structural properties, we also calculate the electronic band dispersion, net magnetic moment, charge transfer, work function, and dipole moment of the metal adsorbed silicene sheets. Alkali metals, Li, Na, and K, adsorb to hollow sites without any lattice distortion. As a consequence of the significant charge transfer from alkalis to silicene, metalization of silicene takes place. Trends directly related to atomic size, adsorption height, work function, and dipole moment of the silicene/alkali adatom system are also revealed. We found that the adsorption of alkaline-earth metals on silicene is entirely different from their adsorption on graphene. The adsorption of Be, Mg, and Ca turns silicene into a narrow gap semiconductor. Adsorption characteristics of eight transition metals Ti, V, Cr, Mn, Fe, Co, Mo, and W are also investigated. As a result of their partially occupied d orbital, transition metals show diverse structural, electronic, and magnetic properties. Upon the adsorption of transition metals, depending on the adatom type and atomic radius, the system can exhibit metal, half-metal, and semiconducting behavior. For all metal adsorbates, the direction of the charge transfer is from adsorbate to silicene, because of its high surface reactivity. Our results indicate that the reactive crystal structure of silicene provides a rich playground for functionalization at nanoscale.

  6. Metal-Silicate Segregation in Deforming Dunitic Rocks: Applications to Core Formation in Europa and Ganymede

    NASA Technical Reports Server (NTRS)

    Hustoft, J. W.; Kohlstedt, D. L.

    2004-01-01

    Core formation is an important event in the evolution of a planetary body, affecting both the geochemical and geophysical properties of the body. Metal-silicate segregation could have proceeded either by settling of liquid metal through a magma ocean or by percolation of liquid metal through a solid silicate mantle. Percolation of metallic melt had previously been excluded as a viable segregation mechanism because metallic melts do not form an interconnected network under hydrostatic conditions, except at high melt fraction (>5 vol%), due to the high dihedral angle between metals and silicates (>60 ). Without an interconnected network, porous flow of metallic melt is impossible, leaving the magma ocean scenario as the only mechanism to form the core. Moment-of-inertia measurements of Europa and Ganymede from the Galileo probe indicate that they are differentiated. This evidence suggests that a method for segregating metals and silicates at temperatures low enough to retain volatile compounds must exist. We have investigated the effect of deformation on the distribution of metallic melts in silicates. We have deformed samples of olivine + 5-9 vol% Fe-S to strains of 2.5 in simple shear and find that the metallic melt segregates into melt-rich planes oriented at 20 to the shear plane. These metallic melt-rich bands are similar in structure to the silicate melt-rich bands reported by Holtzman, indicating that deformation can interconnect isolated metallic melt pockets and allow porous flow of non-wetting melts. Such a core formation process could have occurred in the jovian satellites.

  7. Secondary cell with orthorhombic alkali metal/manganese oxide phase active cathode material

    DOEpatents

    Doeff, M.M.; Peng, M.Y.; Ma, Y.; Visco, S.J.; DeJonghe, L.C.

    1996-09-24

    An alkali metal manganese oxide secondary cell is disclosed which can provide a high rate of discharge, good cycling capabilities, good stability of the cathode material, high specific energy (energy per unit of weight) and high energy density (energy per unit volume). The active material in the anode is an alkali metal and the active material in the cathode comprises an orthorhombic alkali metal manganese oxide which undergoes intercalation and deintercalation without a change in phase, resulting in a substantially linear change in voltage with change in the state of charge of the cell. The active material in the cathode is an orthorhombic structure having the formula M{sub x}Z{sub y}Mn{sub (1{minus}y)}O{sub 2}, where M is an alkali metal; Z is a metal capable of substituting for manganese in the orthorhombic structure such as iron, cobalt or titanium; x ranges from about 0.2 in the fully charged state to about 0.75 in the fully discharged state, and y ranges from 0 to 60 atomic %. Preferably, the cell is constructed with a solid electrolyte, but a liquid or gelatinous electrolyte may also be used in the cell. 11 figs.

  8. Secondary cell with orthorhombic alkali metal/manganese oxide phase active cathode material

    DOEpatents

    Doeff, Marca M.; Peng, Marcus Y.; Ma, Yanping; Visco, Steven J.; DeJonghe, Lutgard C.

    1996-01-01

    An alkali metal manganese oxide secondary cell is disclosed which can provide a high rate of discharge, good cycling capabilities, good stability of the cathode material, high specific energy (energy per unit of weight) and high energy density (energy per unit volume). The active material in the anode is an alkali metal and the active material in the cathode comprises an orthorhombic alkali metal manganese oxide which undergoes intercalation and deintercalation without a change in phase, resulting in a substantially linear change in voltage with change in the state of charge of the cell. The active material in the cathode is an orthorhombic structure having the formula M.sub.x Z.sub.y Mn.sub.(1-y) O.sub.2, where M is an alkali metal; Z is a metal capable of substituting for manganese in the orthorhombic structure such as iron, cobalt or titanium; x ranges from about 0.2 in the fully charged state to about 0.75 in the fully discharged state, and y ranges from 0 to 60 atomic %. Preferably, the cell is constructed with a solid electrolyte, but a liquid or gelatinous electrolyte may also be used in the cell.

  9. Determining the Metal/Silicate Partition Coefficient of Germanium: Implications for Core and Mantle Differentiation.

    NASA Technical Reports Server (NTRS)

    King, C.; Righter, K.; Danielson, L.; Pando, K.; Lee, C.

    2010-01-01

    Currently there are several hypotheses for the thermal state of the early Earth. Some hypothesize a shallow magma ocean, or deep magma ocean, or heterogeneous accretion which requires no magma ocean at all. Previous models are unable to account for Ge depletion in Earth's mantle relative to CI chondrites. In this study, the element Ge is used to observe the way siderophile elements partition into the metallic core. The purpose of this research is to provide new data for Ge and to further test these models for Earth's early stages. The partition coefficients (D(sub Ge) = c(sub metal)/c(sub silicate), where D = partition coefficient of Ge and c = concentration of Ge in the metal and silicate, respectively) of siderophile elements were studied by performing series of high pressure, high temperature experiments. They are also dependent on oxygen fugacity, and metal and silicate composition. Ge is a moderately siderophile element found in both the mantle and core, and has yet to be studied systematically at high temperatures. Moreover, previous work has been limited by the low solubility of Ge in silicate melts (less than 100 ppm and close to detection limits for electron microprobe analysis). Reported here are results from 14 experiments studying the partitioning of Ge between silicate and metallic liquids. The Ge concentrations were then analyzed using Laser Ablation Inductively Coupled Mass Spectrometry (LA-ICP-MS) which is sensitive enough to detect ppm levels of Ge in the silicate melt.

  10. Theoretical study on the adsorption of carbon dioxide on individual and alkali-metal doped MOF-5s

    NASA Astrophysics Data System (ADS)

    Ha, Nguyen Thi Thu; Lefedova, O. V.; Ha, Nguyen Ngoc

    2016-01-01

    Density functional theory (DFT) calculations were performed to investigate the adsorption of carbon dioxide (CO2) on metal-organic framework (MOF-5) and alkali-metal (Li, K, Na) doped MOF-5s. The adsorption energy calculation showed that metal atom adsorption is exothermic in MOF-5 system. Moreover, alkali-metal doping can significantly improve the adsorption ability of carbon dioxide on MOF-5. The best influence is observed for Li-doping.

  11. The Alkali Metal Thermal-To-Electric Converter for Solar System Exploration

    NASA Technical Reports Server (NTRS)

    Ryan, M.

    1999-01-01

    AMTEC, the Alkali Metal Thermal to Electric Converter, is a direct thermal to electric energy conversion device; it has been demostrated to perform at high power densities, with open circuit voltages in single electrochemical cells up to 1.6 V and current desities up to 2.0 A/cm(sup 2).

  12. Oxygen production by molten alkali metal salts using multiple absorption-desorption cycles

    DOEpatents

    Cassano, A.A.

    1985-07-02

    A continuous chemical air separation is performed wherein oxygen is recovered with a molten alkali metal salt oxygen acceptor in a series of absorption zones which are connected to a plurality of desorption zones operated in separate parallel cycles with the absorption zones. A greater recovery of high pressure oxygen is achieved at reduced power requirements and capital costs. 3 figs.

  13. Oxygen production by molten alkali metal salts using multiple absorption-desorption cycles

    DOEpatents

    Cassano, Anthony A.

    1985-01-01

    A continuous chemical air separation is performed wherein oxygen is recovered with a molten alkali metal salt oxygen acceptor in a series of absorption zones which are connected to a plurality of desorption zones operated in separate parallel cycles with the absorption zones. A greater recovery of high pressure oxygen is achieved at reduced power requirements and capital costs.

  14. Unidirectional thermal expansion in KZnB3O6: role of alkali metals.

    PubMed

    Lou, Yanfang; Li, Dandan; Li, Zhilin; Zhang, Han; Jin, Shifeng; Chen, Xiaolong

    2015-12-14

    The driving force of the unidirectional thermal expansion in KZnB3O6 has been studied experimentally and theoretically. Our results show that the low-energy vibrational modes of alkali metals play a crucial role in this unusual thermal behavior. PMID:26515521

  15. Enhancing electrocatalytic hydrogen evolution by nickel salicylaldimine complexes with alkali metal cations in aqueous media.

    PubMed

    Shao, Haiyan; Muduli, Subas K; Tran, Phong D; Soo, Han Sen

    2016-02-18

    New salicylaldimine nickel complexes, comprising only earth-abundant elements, have been developed for electrocatalytic hydrogen evolution in aqueous media. The second-sphere ether functionalities on the periphery of the complexes enhance the electrocatalytic activity in the presence of alkali metal cations. The electrocatalysts demonstrate improved performances especially in the economical and sustainable seawater reaction medium. PMID:26779580

  16. Characterization of lanthanide(III) DOTP complexes: Thermodynamics, protonation, and coordination to alkali metal ions

    SciTech Connect

    Sherry, A.D.; Ren, J.; Huskens, J.

    1996-07-31

    The chemical and thermodynamic characterization of Lanthanide(III) DOTP complexes was performed. Spectrophotometry, potentiometry, osmometry, and NMR spectroscopy were used in this characterization. Stability constants, protonation equilibria, and interactions of the complexes with alkali metal ions were measured and summarized.

  17. Affinity Capillary Electrophoresis Applied to Investigation of Valinomycin Complexes with Ammonium and Alkali Metal Ions.

    PubMed

    Štěpánová, Sille; Kašička, Václav

    2016-01-01

    This chapter deals with the application of affinity capillary electrophoresis (ACE) to investigation of noncovalent interactions (complexes) of valinomycin, a macrocyclic dodecadepsipeptide antibiotic ionophore, with ammonium and alkali metal ions (lithium, sodium, potassium, rubidium, and cesium). The strength of these interactions was characterized by the apparent binding (stability, association) constants (K b) of the above valinomycin complexes using the mobility shift assay mode of ACE. The study involved measurements of effective electrophoretic mobility of valinomycin at variable concentrations of ammonium or alkali metal ions in the background electrolyte (BGE). The effective electrophoretic mobilities of valinomycin measured at ambient temperature and variable ionic strength were first corrected to the reference temperature 25 °C and constant ionic strength (10 or 25 mM). Then, from the dependence of the corrected valinomycin effective mobility on the ammonium or alkali metal ion concentration in the BGE, the apparent binding constants of the valinomycin-ammonium or valinomycin-alkali metal ion complexes were determined using a nonlinear regression analysis. Logarithmic form of the binding constants (log K b) were found to be in the range of 1.50-4.63, decreasing in the order Rb(+) > K(+) > Cs(+) > > Na(+) > NH4 (+) ~ Li(+). PMID:27473493

  18. The interactions of sorbates with gallosilicates and alkali-metal exchanged gallosilicates

    NASA Astrophysics Data System (ADS)

    Limtrakul, J.; Kuno, M.; Treesukol, P.

    1999-11-01

    Structures, energetics and vibrational frequencies of the interaction of adsorbates with H-aluminosilicates (H-AlZ), H-gallosilicates (H-GaZ), alkali-metal exchanged aluminosilicates (X-AlZ) and alkali-metal exchanged gallosilicates (X-GaZ), where X being Li, Na, or K, have been carried out at B3LYP and HF levels of theory with 6-31G(d) as the basis set. The charge compensating alkali-metal ions can affect the catalytically active site (Si-O-T where T=Al or Ga) by weakening the Si-O, Al-O, and Ga-O bonds as compared to their anionic frameworks. Comparing the net stabilization energies, Δ ENSE, of the naked alkali-metal/H 2O adducts with those of the alkali-metal exchanged zeolite/H 2O systems, the latter amounts only to about 50% of the former, which is partly due to the destabilizing role of the negative zeolitic oxygen frameworks surrounding the cations. The interaction of sorbates with the alkali-metal exchanged gallosilicates can be employed to probe the field strength inside the catalytic frameworks as indicated by the plot of the binding energy, Δ E, versus 1/ RX-O w2, with R(X-O w) being the distance between the cationic nucleus and the oxygen atom of the adsorbate. The IR spectra of H 2O adsorbed on Na-AlZ are calculated to be 3584, 3651, and 1686 cm -1. The obtained results are in excellent agreement with the very recent experimental IR spectra of water adsorbed on Na-ZSM-5 of Zecchina et al. (J. Phys. Chem., 100 (1996) 16 484). Other important features, i.e. the correlation between Δ νOH and, Δ E, R(X-O w) , and 1/ RX-O w2, cationic size, demonstrate that the interactions of sorbates with alkali-metal exchanged gallosilicates are well approximated by electrostatic contribution.

  19. Alkali Metal Carbenoids: A Case of Higher Stability of the Heavier Congeners.

    PubMed

    Molitor, Sebastian; Gessner, Viktoria H

    2016-06-27

    As a result of the increased polarity of the metal-carbon bond when going down the group of the periodic table, the heavier alkali metal organyl compounds are generally more reactive and less stable than their lithium congeners. We now report a reverse trend for alkali metal carbenoids. Simple substitution of lithium by the heavier metals (Na, K) results in a significant stabilization of these usually highly reactive compounds. This allows their isolation and handling at room temperature and the first structure elucidation of sodium and potassium carbenoids. The control of stability was used to control reactivity and selectivity. Hence, the Na and K carbenoids act as selective carbene-transfer reagents, whereas the more labile lithium systems give rise to product mixtures. Additional fine tuning of the M-C interaction by means of crown ether addition further allows for control of the stability and reactivity. PMID:27100278

  20. Theory of magic optical traps for Zeeman-insensitive clock transitions in alkali-metal atoms

    SciTech Connect

    Derevianko, Andrei

    2010-05-15

    Precision measurements and quantum-information processing with cold atoms may benefit from trapping atoms with specially engineered, 'magic' optical fields. At the magic trapping conditions, the relevant atomic properties remain immune to strong perturbations by the trapping fields. Here we develop a theoretical analysis of magic trapping for especially valuable Zeeman-insensitive clock transitions in alkali-metal atoms. The involved mechanism relies on applying a magic bias B field along a circularly polarized trapping laser field. We map out these B fields as a function of trapping laser wavelength for all commonly used alkalis. We also highlight a common error in evaluating Stark shifts of hyperfine manifolds.

  1. Depletion of Vandium in Planetary Mantles: Controlled by Metal, Oxide, or Silicate?

    NASA Technical Reports Server (NTRS)

    Righter, Kevin

    2006-01-01

    Vanadium concentrations in planetary mantles can provide information about the conditions during early accretion and differentiation. Because V is a slightly siderophile element, it is usually assumed that any depletion would be due to core formation and metal-silicate equilibrium. However, V is typically more compatible in phases such as spinel, magnesiowuestite and garnet. Fractionation of all of these phases would cause depletions more marked than those from metal. In this paper consideration of depletions due to metal, oxide and silicate are critically evaluated.

  2. Potassium silicate-zinc oxide solution for metal finishes

    NASA Technical Reports Server (NTRS)

    Schutt, J. B.

    1970-01-01

    Examples of zinc dust formulations, which are not subject to cracking or crazing, are fire retardant, and have high adhesive qualities, are listed. The potassium silicate in these formulations has mol ratios of dissolved silica potassium oxide in the range 4.8 to 1 - 5.3 to 1.

  3. Pt, Au, Pd and Ru Partitioning Between Mineral and Silicate Melts: The Role of Metal Nanonuggets

    NASA Technical Reports Server (NTRS)

    Malavergne, V.; Charon, E.; Jones, J.; Agranier, A.; Campbell, A.

    2012-01-01

    The partition coefficients of Pt and other Pt Group Elements (PGE) between metal and silicate D(sub Metal-Silicate) and also between silicate minerals and silicate melts D(sub Metal-Silicate) are among the most challenging coefficients to obtain precisely. The PGE are highly siderophile elements (HSE) with D(sub Metal-Silicate) >10(exp 3) due to the fact that their concentrations in silicates are very low (ppb to ppt range). Therefore, the analytical difficulty is increased by the possible presence of HSE-rich-nuggets in reduced silicate melts during experiments). These tiny HSE nuggets complicate the interpretation of measured HSE concentrations. If the HSE micro-nuggets are just sample artifacts, then their contributions should be removed before calculations of the final concentration. On the other hand, if they are produced during the quench, then they should be included in the analysis. We still don't understand the mechanism of nugget formation well. Are they formed during the quench by precipitation from precursor species dissolved homogeneously in the melts, or are they precipitated in situ at high temperature due to oversaturation? As these elements are important tracers of early planetary processes such as core formation, it is important to take up this analytical and experimental challenge. In the case of the Earth for example, chondritic relative abundances of the HSE in some mantle xenoliths have led to the concept of the "late veneer" as a source of volatiles (such as water) and siderophiles in the silicate Earth. Silicate crystal/liquid fractionation is responsible for most, if not all, the HSE variation in the martian meteorite suites (SNC) and Pt is the element least affected by these fractionations. Therefore, in terms of reconstructing mantle HSE abundances for Mars, Pt becomes a very important player. In the present study, we have performed high temperature experiments under various redox conditions in order to determine the abundances of Pt, Au

  4. Conduit entrainment surrounding sinking metal-silicate plumes during core formation

    NASA Astrophysics Data System (ADS)

    Klein, S. M.; Brand, D.; Weeraratne, D. S.

    2014-12-01

    Although the Earth today is segregated into two distinct compositional regions of a silicate mantle and metallic core, the process of differentiation from their original chondritic form is not clear. Continuous meteorite bombardment melted impactors and target bodies causing dissociation of metal from silicates which may have formed magma reservoirs or oceans. The heavy liquid metal phase will sink quickly through a silicate magma ocean and settle at the base as a metal pond. A high density metal pond will be unstable and is expected to sink as a Rayleigh-Taylor instability descending as liquid metal plumes to the core. Previous experiments have shown that lighter silicate material from the magma ocean becomes entrained as a conduit that trails behind sinking metal diapirs. These silicates are then transported to the base of the mantle with implications for mantle and core composition. We perform laboratory fluid experiments which model this process of entrainment and differentiation using glass and gallium spheres in high viscosity liquid sucrose solutions. We use high speed photography and dye to visualize and measure conduit formation and entrainment surrounding a descending sphere. Preliminary experiments indicate that the volume of material that surrounds a sphere is highest at the top of the box when the sphere begins its descent. As the sphere sinks, the entrainment of dyed fluid around the sphere decreases exponentially with falling distance. We suggest this is the result of drag forces acting on walls of the conduit. The volume of entrained material reduces by 80% in the upper 1/3 of the drop trajectory. As much as 8-10% of the original fluid volume is carried to the base of the box and will segregate from the sphere or diffuse after it settles. Higher viscosity fluids are observed to entrain more material on average compared to lower viscosity fluids. These results have important implications for delivery of silicate materials to the base of the mantle

  5. 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. PMID:26005925

  6. Alkali-Metal-Ion-Assisted Hydrogen Atom Transfer in the Homocysteine Radical.

    PubMed

    Lesslie, Michael; Lau, Justin Kai-Chi; Lawler, John T; Siu, K W Michael; Oomens, Jos; Berden, Giel; Hopkinson, Alan C; Ryzhov, Victor

    2016-02-12

    Intramolecular hydrogen atom transfer (HAT) was examined in homocysteine (Hcy) thiyl radical/alkali metal ion complexes in the gas phase by combination of experimental techniques (ion-molecule reactions and infrared multiple photon dissociation spectroscopy) and theoretical calculations. The experimental results unequivocally show that metal ion complexation (as opposed to protonation) of the regiospecifically generated Hcy thiyl radical promotes its rapid isomerisation into an α-carbon radical via HAT. Theoretical calculations were employed to calculate the most probable HAT pathway and found that in alkali metal ion complexes the activation barrier is significantly lower, in full agreement with the experimental data. This is, to our knowledge, the first example of a gas-phase thiyl radical thermal rearrangement into an α-carbon species within the same amino acid residue and is consistent with the solution phase behaviour of Hcy radical. PMID:26836574

  7. Structure and properties of alizarin complex formed with alkali metal hydroxides in methanol solution.

    PubMed

    Jeliński, Tomasz; Cysewski, Piotr

    2016-06-01

    Quantum chemical computations were used for prediction of the structure and color of alizarin complex with alkali metal hydroxides in methanolic solutions. The color prediction relying on the single Gaussian-like band once again proved the usefulness of the PBE0 density functional due to the observed smallest color difference between computed and experimentally derived values. It was found that the alkali metal hydroxide molecules can bind to the two oxygen atoms of both hydroxyl groups of alizarin or to one of these atoms and the oxygen atom from the keto group in a complex with three methanol molecules. This means that two electronic transitions need to be taken into account when considering the spectra of the studied complexes. The resulting bond lengths and angles are correlated with the properties of the alkali metal atoms. The molar mass, the atomic radius, and the Pauling electronegativity of studied metals are quite accurate predictors of the geometric properties of hydroxide complexes with alizarin in methanol solution. Graphical abstract The spectra of the neutral and monoanionic form of alizarin together with color changes resulting from addition of different metal hydroxides and represented in CIE color space. PMID:27178415

  8. Compliant alkali silicate sealing glass for solid oxide fuel cell applications: Combined stability in isothermal ageing and thermal cycling with YSZ coated ferritic stainless steels

    SciTech Connect

    Chou, Y. S.; Thomsen, Edwin C.; Choi, Jung-Pyung; Stevenson, Jeffry W.

    2012-01-01

    An alkali-containing silicate glass (SCN-1) is currently being evaluated as a candidate sealing glass for solid oxide fuel cell (SOFC) applications. The glass contains about 17 mole% alkalis (K+Na) and has low glass transition and softening temperatures. It remains vitreous and compliant around 750-800oC after sealing without substantial crystallization, as contrary to conventional glass-ceramic sealants, which experience rapid crystallization after the sealing process. The glassy nature and low characteristic temperatures can reduce residual stresses and result in the potential for crack healing. In a previous study, the glass was found to have good thermal cycle stability and was chemically compatible with YSZ coating during short term testing. In the current study, the compliant glass was further evaluated in a more realistic way in that the sealed glass couples were first isothermally aged for 1000h followed by thermal cycling. High temperature leakage was measured. The chemical compatibility was also investigated with powder mixtures at 700 and 800oC to enhance potential interfacial reaction. In addition, interfacial microstructure was examined with scanning electron microscopy and evaluated with regard to the leakage and chemical compatibility results.

  9. Calculation of Oxygen Fugacity in High Pressure Metal-Silicate Experiments and Comparison to Standard Approaches

    NASA Technical Reports Server (NTRS)

    Righter, K.; Ghiorso, M.

    2009-01-01

    Calculation of oxygen fugacity in high pressure and temperature experiments in metal-silicate systems is usually approximated by the ratio of Fe in the metal and FeO in the silicate melt: (Delta)IW=2*log(X(sub Fe)/X(sub FeO)), where IW is the iron-wustite reference oxygen buffer. Although this is a quick and easy calculation to make, it has been applied to a huge variety of metallic (Fe- Ni-S-C-O-Si systems) and silicate liquids (SiO2, Al2O3, TiO2, FeO, MgO, CaO, Na2O, K2O systems). This approach has surely led to values that have little meaning, yet are applied with great confidence, for example, to a terrestrial mantle at "IW-2". Although fO2 can be circumvented in some cases by consideration of Fe-M distribution coefficient, these do not eliminate the effects of alloy or silicate liquid compositional variation, or the specific chemical effects of S in the silicate liquid, for example. In order to address the issue of what the actual value of fO2 is in any given experiment, we have calculated fO2 from the equilibria 2Fe (metal) + SiO2 (liq) + O2 = Fe2SiO4 (liq).

  10. Metal-Silicate Partitioning of Tungsten from 10 to 50 GPa

    NASA Technical Reports Server (NTRS)

    Shofner, G. A.; Campbell, A. J.; Danielson, L.; Rahman, Z.; Righter, K.

    2014-01-01

    Geochemical models of core formation are commonly based on core and mantle abundances of siderophile elements that partitioned between silicate and metal in a magma ocean in the early Earth. Tungsten is a moderately siderophile element that may provide constraints on the pressure, temperature, composition, and oxygen fugacity conditions, and on the timing of core formation in the Earth. Previous experimental studies suggest that pressure exerts little to no influence over W metal-silicate partitioning up to 24 GPa, and indicate that the stronger influences are temperature, composition, and oxygen fugacity. However, core formation models based in part on W, predict metal-silicate equilibration pressures outside the available experimental pressure range, requiring extrapolation of parameterized models. Therefore, higher pressure experimental data on W were needed to constrain this important parameter.

  11. Ab Initio Molecular Dynamics of Dimerization and Clustering in Alkali Metal Vapors.

    PubMed

    Chaban, Vitaly V; Prezhdo, Oleg V

    2016-06-30

    Alkali metals are known to form dimers, trimers, and tetramers in their vapors. The mechanism and regularities of this phenomenon characterize the chemical behavior of the first group elements. We report ab initio molecular dynamics (AIMD) simulations of the alkali metal vapors and characterize their structural properties, including radial distribution functions and atomic cluster size distributions. AIMD confirms formation of Men, where n ranges from 2 to 4. High pressure sharply favors larger structures, whereas high temperature decreases their fraction. Heavier alkali metals maintain somewhat larger fractions of Me2, Me3, and Me4, relative to isolated atoms. A single atom is the most frequently observed structure in vapors, irrespective of the element and temperature. Due to technical difficulties of working with high temperatures and pressures in experiments, AIMD is the most affordable method of research. It provides valuable understanding of the chemical behavior of Li, Na, K, Rb, and Cs, which can lead to development of new chemical reactions involving these metals. PMID:27294399

  12. Buffer-gas-induced shift and broadening of hyperfine resonances in alkali-metal vapors

    NASA Astrophysics Data System (ADS)

    Oreto, P. J.; Jau, Y.-Y.; Post, A. B.; Kuzma, N. N.; Happer, W.

    2004-04-01

    We review the shift and broadening of hyperfine resonance lines of alkali-metal atoms in buffer gases. We present a simple theory both for the shift and the broadening induced by He gas. The theory is parametrized by the scattering length of slow electrons on He atoms and by the measured hyperfine intervals and binding energies of the S states of alkali-metal atoms. The calculated shifts and their temperature dependence are in good agreement with the published experimental data. The calculated broadening is 1.6 times smaller than the recent measurements, and more than 20 times smaller than the earlier measurements. We attribute much of the linewidth in the earlier experiments to possible small temperature gradients and the resulting inhomogeneous line broadening from the temperature dependence of hyperfine frequency shift at constant buffer-gas pressure.

  13. Theory of metal atom-water interactions and alkali halide dimers

    NASA Technical Reports Server (NTRS)

    Jordan, K. D.; Kurtz, H. A.

    1982-01-01

    Theoretical studies of the interactions of metal atoms with water and some of its isoelectronic analogs, and of the properties of alkali halides and their aggregates are discussed. Results are presented of ab initio calculations of the heats of reaction of the metal-water adducts and hydroxyhydrides of Li, Be, B, Na, Mg, and Al, and of the bond lengths and angles an; the heats of reaction for the insertion of Al into HF, H2O, NH3, H2S and CH3OH, and Be and Mg into H2O. Calculations of the electron affinities and dipole moments and polarizabilities of selected gas phase alkali halide monomers and dimers are discussed, with particular attention given to results of calculations of the polarizability of LiF taking into account electron correlation effects, and the polarizability of the dimer (LiF)2.

  14. An optically trapped mixture of alkali-metal and metastable helium atoms

    NASA Astrophysics Data System (ADS)

    Flores, Adonis; Mishra, Hari Prasad; Vassen, Wim; Knoop, Steven

    2016-05-01

    Ultracold collisions between alkali-metal and metastable triplet helium (He*) atoms provide the opportunity to study Feshbach resonances in the presence of a strong loss channel, namely Penning ionization, which strongly depends on the internal spin-states of the atoms. Recently we have realized the first optically trapped alkali-metal-metastable helium mixture. To prepare the ultracold 87 Rb+4 He* mixture in a single beam optical dipole trap (ODT), we apply evaporative cooling in a strong quadrupole magnetic trap (QMT) for both species and subsequent transfer to the ODT via a hybrid trap. We will present lifetime measurements of different spin-state mixtures, testing the application of the universal loss model to this interesting multichannel collision system.

  15. 'Doubly Magic' Conditions in Magic-Wavelength Trapping of Ultracold Alkali-Metal Atoms

    SciTech Connect

    Derevianko, Andrei

    2010-07-16

    In experiments with trapped atoms, atomic energy levels are shifted by the trapping optical and magnetic fields. Regardless of this strong perturbation, precision spectroscopy may be still carried out using specially crafted, 'magic' trapping fields. Finding these conditions for particularly valuable microwave transitions in alkali-metal atoms has so far remained an open challenge. Here I demonstrate that the microwave transitions in alkali-metal atoms may be indeed made impervious to both trapping laser intensity and fluctuations of magnetic fields. I consider driving multiphoton transitions between the clock levels and show that these 'doubly magic' conditions are realized at special values of trapping laser wavelengths and fixed values of relatively weak magnetic fields. This finding has implications for precision measurements and quantum information processing with qubits stored in hyperfine manifolds.

  16. X-ray Compton scattering experiments for fluid alkali metals at high temperatures and pressures

    SciTech Connect

    Matsuda, K. Fukumaru, T.; Kimura, K.; Yao, M.; Tamura, K.; Katoh, M.; Kajihara, Y.; Inui, M.; Itou, M.; Sakurai, Y.

    2015-08-17

    We have developed a high-pressure vessel and a cell for x-ray Compton scattering measurements of fluid alkali metals. Measurements have been successfully carried out for alkali metal rubidium at elevated temperatures and pressures using synchrotron radiation at SPring-8. The width of Compton profiles (CPs) of fluid rubidium becomes narrow with decreasing fluid density, which indicates that the CPs sensitively detect the effect of reduction in the valence electron density. At the request of all authors of the paper, and with the agreement of the Proceedings Editor, an updated version of this article was published on 10 September 2015. The original article supplied to AIP Publishing was not the final version and contained PDF conversion errors in Formulas (1) and (2). The errors have been corrected in the updated and re-published article.

  17. Reactions between cold methyl halide molecules and alkali-metal atoms

    SciTech Connect

    Lutz, Jesse J.; Hutson, Jeremy M.

    2014-01-07

    We investigate the potential energy surfaces and activation energies for reactions between methyl halide molecules CH{sub 3}X (X = F, Cl, Br, I) and alkali-metal atoms A (A = Li, Na, K, Rb) using high-level ab initio calculations. We examine the anisotropy of each intermolecular potential energy surface (PES) and the mechanism and energetics of the only available exothermic reaction pathway, CH{sub 3}X + A → CH{sub 3} + AX. The region of the transition state is explored using two-dimensional PES cuts and estimates of the activation energies are inferred. Nearly all combinations of methyl halide and alkali-metal atom have positive barrier heights, indicating that reactions at low temperatures will be slow.

  18. Calculation of radiative corrections to hyperfine splittings in the neutral alkali metals

    SciTech Connect

    Sapirstein, J.; Cheng, K.T.

    2003-02-01

    The radiative correction to hyperfine splitting in hydrogen is dominated by the Schwinger term, {alpha}/2{pi} E{sub F}, where E{sub F} is the lowest-order hyperfine splitting. Binding corrections to this term, which enter as powers and logarithms of Z{alpha}, can be expected to be increasingly important in atoms with higher nuclear charge Z. Methods that include all orders of Z{alpha}, developed first to study highly charged ions, are adapted to the study of the neutral alkali metals, lithium through francium. It is shown that the use of the Schwinger term alone to account for radiative corrections to hyperfine splittings becomes qualitatively incorrect for the heavier alkali metals.0.

  19. An Aqueous Redox Flow Battery Based on Neutral Alkali Metal Ferri/ferrocyanide and Polysulfide Electrolytes

    SciTech Connect

    Wei, Xiaoliang; Xia, Gordon; Kirby, Brent W.; Thomsen, Edwin C.; Li, Bin; Nie, Zimin; Graff, Gordon L.; Liu, Jun; Sprenkle, Vincent L.; Wang, Wei

    2015-11-13

    Aiming to explore low-cost redox flow battery systems, a novel iron-polysulfide (Fe/S) flow battery has been demonstrated in a laboratory cell. This system employs alkali metal ferri/ferrocyanide and alkali metal polysulfides as the redox electrolytes. When proper electrodes, such as pretreated graphite felts, are used, 78% energy efficiency and 99% columbic efficiency are achieved. The remarkable advantages of this system over current state-of-the-art redox flow batteries include: 1) less corrosive and relatively environmentally benign redox solutions used; 2) excellent energy and utilization efficiencies; 3) low cost for redox electrolytes and cell components. These attributes can lead to significantly reduced capital cost and make the Fe/S flow battery system a promising low-cost energy storage technology. The major drawbacks of the present cell design are relatively low power density and possible sulfur species crossover. Further work is underway to address these concerns.

  20. Metal-silicate partitioning of lithophile elements at high pressures and temperatures

    NASA Astrophysics Data System (ADS)

    Chidester, B.; Rahman, Z.; Righter, K.; Campbell, A. J.

    2015-12-01

    Trace element abundances in Earth's core were established during core-mantle differentiation and metal-silicate equilibration processes early in the planet's history. The core has been suggested as a possible reservoir in which the presence of nominally lithophile elements can explain the observance of non-chondritic ratios of some of these elements in surface rocks (e.g. Nb/Ta, Th/U and Mg/Si)[1-2]. Additionally, several of these elements (U, Th and K) are long-lived sources of radiogenic heat and could be important for explaining the geomagnetic field early in Earth's history. Based on their metal-silicate partitioning behavior at near ambient conditions, it is frequently assumed that uranium and other strongly lithophile elements are present in the core at only trivial abundances. However, core formation took place at a variety of conditions, reaching pressures and temperatures well above those in which most metal-silicate partitioning measurements were obtained[3]. Here we report metal-silicate partitioning data of lithophile elements such as U and Mg, as well as partially siderophile elements Si and S, at conditions more relevant to metal segregation and core formation in a magma ocean. Laser heated diamond anvil methods were used to obtain pressures of 30-70 GPa and temperatures up to 5200 K. FIB/EM methods were used to section the recovered samples and measure the quenched metal and silicate melt compositions. We find that even strongly lithophile elements such as U and Mg partition measurably into the metal phase under extreme P-T conditions. References: [1]Wade, J. and Wood, B. J., Nature, 109 (2001) [2]Allegre et al. EPSL, 134 (1995) [3]Rubie, et al. Icarus, 248 (2015)

  1. High field superconductivity in alkali metal intercalates of MoS2

    NASA Technical Reports Server (NTRS)

    Woollam, J. A.; Flood, D. J.; Wagoner, D. E.; Somoano, R. B.; Rembaum, A.

    1973-01-01

    In the search for better high temperature, high critical field superconductors, a class of materials was found which have layered structures and can be intercalated with various elements and compounds. Since a large number of compounds can be formed, intercalation provides a method of control of superconducting properties. They also provide the possible medium for excitonic superconductivity. Results of magnetic field studies are presented on alkali metal (Na, K, Rb, and Cs) intercalated MoS2 (2H polymorph).

  2. Development of processes for the production of solar grade silicon from halides and alkali metals

    NASA Technical Reports Server (NTRS)

    Dickson, C. R.; Gould, R. K.

    1980-01-01

    High temperature reactions of silicon halides with alkali metals for the production of solar grade silicon in volume at low cost were studied. Experiments were performed to evaluate product separation and collection processes, measure heat release parameters for scaling purposes, determine the effects of reactants and/or products on materials of reactor construction, and make preliminary engineering and economic analyses of a scaled-up process.

  3. Equation of state for solid rare gases and alkali metals under pressure

    NASA Astrophysics Data System (ADS)

    Bonnet, Pierre

    2016-07-01

    This investigation is based on an atomic equation of state which takes into account the excluded volume of the atom being considered. Study of solid rare gases allows following the packing factor of the solid in equilibrium with the gas at different temperatures and of the solid and the liquid in the case of solid-liquid equilibria. The application of a pressure to the solid up to 9800 MPa allows determining the decrease in atomic volume and thus the compressibility. Such a study leads to proposing a new expression through dividing the pressure derivative (as a function of the excluded volume) by the pressure. This new coefficient is a pressure-independent constant but varies with the atom considered. Multiplied by the initial atomic volume, this coefficient has a unique value for all the rare gases. Furthermore, this is also true for the series of alkali metals with however a lower value of the coefficient. The atomic configurations of the two series are very different with one free electron for the alkali metals but closed shells for the rare gases. The alkali metals are therefore more complex than the rare gases. It is worthwhile to note that study of the equilibrium has not required the use of the principles of thermodynamics.

  4. A hexagonal structure for alkali-metal doped poly (p-phenylene)

    NASA Astrophysics Data System (ADS)

    Murthy, N. S.; Baughman, R. H.; Shacklette, L. W.; Fark, H.; Fink, J.

    1991-05-01

    An hexagonal structure (space group p overline62m, a = 8.6 Å) is proposed for sodium-doped poly(p-phenylene), PPP. The diffraction pattern calculated using only one freely adjustable parameter (the distance between the alkali-metal column and the polymer backbone) is in good agreement with the observed electron diffraction patterns. A similar structure ( a = 9.2 Å) is also suggested by diffraction data for potassium-doped PPP. This hexagonal structure is analogous to that reported for sodium-doped poly(p-phenylene vinylene), lithium-doped polyacetylene, and sodium-doped polyacetylene. The three chain per column arrangement provides a fundamental structural motif which maximizes the coordination of the negatively charged carbon atoms with both the alkali metal ions and the hydrogens, and maximizes interchain, intercolumn, and hydrogen to alkali-metal separations. The size of the dopant-ion relative to the cross-sectional dimensions of the host polymer determines whether the dopant-ion columns are formed in triangular (three chain per column) or tetragonal (four chain per column) channels.

  5. Ultrafine Na-4-mica: uptake of alkali and alkaline earth metal cations by ion exchange.

    PubMed

    Kodama, Tatsuya; Ueda, Masahito; Nakamuro, Yumiko; Shimizu, Ken-ichi; Komarneni, Sridhar

    2004-06-01

    The cation exchange properties of alkali and alkaline earth metal cations at room temperature were investigated on an ultrafine, highly charged Na-4-mica (with the ideal mica composition Na4Mg6Al4Si4O20F4.xH2O). Ultrafine mica crystallites of 200 nm in size led to faster Sr2+ uptake kinetics in comparison to larger mica crystallites. The alkali metal ion (K+, Cs+, and Li+) exchange uptake was rapid, and complete exchange occurred within 30 min. For the alkaline earth metal ions Ba2+, Ca2+, and Mg2+, however, the exchange uptake required lengthy periods from 3 days to 4 weeks to be completed, similar to its Sr uptake, as previously reported. Kinetic models of the modified Freundlich and parabolic diffusion were examined for the experimental data on the Ba2+, Ca2+, and Mg2+ uptakes. The modified Freundlich model described well the Ba2+ ion uptake kinetics as well as that for the Sr2+ ion, while for the Ca2+ and Mg2+ ions the parabolic diffusion model showed better fitting. The alkali and alkaline earth ion exchange isotherms were also determined in comparison to the Sr2+ exchange isotherm. The thermodynamic equilibria for these cations were compared by using Kielland plots evaluated from the isotherms. PMID:15984251

  6. Secondary nucleation of gibbsite crystals from synthetic Bayer liquors: effect of alkali metal ions

    NASA Astrophysics Data System (ADS)

    Li, Jun; Prestidge, Clive A.; Addai-Mensah, Jonas

    2000-11-01

    The effect of alkali metal ions (Na + versus K +) on secondary nucleation of gibbsite ( γ-Al(OH) 3) from synthetic Bayer liquors has been investigated under seeded, isothermal, batch crystallisation conditions. The nucleation kinetics showed a fourth-order dependence upon Al(III) relative supersaturation and a strong temperature effect. An activation energy of 132 kJ mol -1, which was independent of alkali metal ion, was calculated. Secondary nucleation and subsequent crystal growth rates however, were greater in sodium than in potassium aluminate solution. The Arrhenius, pre-exponential factor was at least three times larger in sodium than in potassium aluminate solutions at equivalent crystal surface area, similar supersaturation and temperature. The results indicated that secondary nucleation of Al(OH) 3 is a chemical reaction-controlled process which is alkali metal ion-mediated. Na + ions provide a more favourable pathway than potassium ions for the formation of Al(III)-containing clusters, higher collision frequency between the species and crystal surface, and faster growth of potential secondary nuclei in the solutions.

  7. Theoretical study of alpha/beta-alanine and their protonated/alkali metal cationized complexes.

    PubMed

    Abirami, S; Xing, Y M; Tsang, C W; Ma, N L

    2005-01-27

    Density functional theory has been employed to model the structure and the relative stabilities of alpha/beta-alanine conformers and their protonated and alkali metal cationized complexes. In general, we find that the behavior of the beta-alanine (beta-Ala) system is quite similar to that of alpha-alanine (alpha-Ala). However, the presence of the methylene group (-CH2-) at the beta position in beta-Ala leads to a few key differences. First, the intramolecular hydrogen bonding patterns are different between free alpha- and beta-Ala. Second, the stability of zwitterionic species (in either the free ligand or alkali metal cationized complexes) is often enhanced in beta-Ala. Third, the preferred mode of alkali metal cation (M+) binding may also differ in alpha- and beta-Ala. Natural energy decomposition analysis has been applied here to gain further insight into the effects of the ligand, cation size, and mode of binding on the nature of interaction in these M+-Ala complexes. PMID:16833371

  8. Isotopic fractionation of alkali earth metals during carbonate precipitation

    NASA Astrophysics Data System (ADS)

    Yotsuya, T.; Ohno, T.; Muramatsu, Y.; Shimoda, G.; Goto, K. T.

    2014-12-01

    The alkaline earth metals such as magnesium, calcium and strontium play an important role in a variety of geochemical and biological processes. The element ratios (Mg/Ca and Sr/Ca) in marine carbonates have been used as proxies for reconstruction of the past environment. Recently several studies suggested that the study for the isotopic fractionation of the alkaline earth metals in marine carbonates has a potentially significant influence in geochemical research fields (e.g. Eisenhauer et al., 2009). The aim of this study is to explore the influence of carbonate polymorphs (Calcite and Aragonite) and environmental factors (e.g., temperature, precipitation rate) on the level of isotopic fractionation of the alkaline earth metals. We also examined possible correlations between the level of isotopic fractionation of Ca and that of other alkaline earth metals during carbonate precipitation. In order to determine the isotope fractionation factor of Mg, Ca and Sr during carbonate precipitation, calcite and aragonite were synthesized from calcium bicarbonate solution in which the amount of magnesium was controlled based on Kitano method. Calcium carbonates were also prepared from the mixture of calcium chlorite and sodium hydrogen carbonate solutions. The isotope fractionation factors were measured by MC-ICPMS. Results suggested that the level of isotopic fractionation of Mg during carbonate precipitation was correlated with that of Sr and that the change of the carbonate crystal structure could make differences of isotopic fractionations of Mg and Ca, however no difference was found in the case of Sr. In this presentation, the possible mechanism will be discussed.

  9. Metal-to-insulator crossover in alkali doped zeolite

    PubMed Central

    Igarashi, Mutsuo; Jeglič, Peter; Krajnc, Andraž; Žitko, Rok; Nakano, Takehito; Nozue, Yasuo; Arčon, Denis

    2016-01-01

    We report a systematic nuclear magnetic resonance investigation of the 23Na spin-lattice relaxation rate, 1/T1, in sodium loaded low-silica X (LSX) zeolite, Nan/Na12-LSX, for various loading levels of sodium atoms n across the metal-to-insulator crossover. For high loading levels of n ≥ 14.2, 1/T1T shows nearly temperature-independent behaviour between 10 K and 25 K consistent with the Korringa relaxation mechanism and the metallic ground state. As the loading levels decrease below n ≤ 11.6, the extracted density of states (DOS) at the Fermi level sharply decreases, although a residual DOS at Fermi level is still observed even in the samples that lack the metallic Drude-peak in the optical reflectance. The observed crossover is a result of a complex loading-level dependence of electric potential felt by the electrons confined to zeolite cages, where the electronic correlations and disorder both play an important role. PMID:26725368

  10. Experimental evidence for Mo isotope fractionation between metal and silicate liquids

    NASA Astrophysics Data System (ADS)

    Hin, Remco C.; Burkhardt, Christoph; Schmidt, Max W.; Bourdon, Bernard; Kleine, Thorsten

    2013-10-01

    Stable isotope fractionation of siderophile elements may inform on the conditions and chemical consequences of core-mantle differentiation in planetary objects. The extent to which Mo isotopes fractionate during such metal-silicate segregation, however, is so far unexplored. We have therefore investigated equilibrium fractionation of Mo isotopes between liquid metal and liquid silicate to evaluate the potential of Mo isotopes as a new tool to study core formation. We have performed experiments at 1400 and 1600 °C in a centrifuging piston cylinder. Tin was used to lower the melting temperature of the Fe-based metal alloys to <1400 °C, while variable Fe-oxide contents were used to vary oxygen fugacity in graphite and MgO capsules. Isotopic analyses were performed using a double spike technique. In experiments performed at 1400 °C, the 98Mo/95Mo ratio of silicate is 0.19±0.03‰ (95% confidence interval) heavier than that of metal. This fractionation is not significantly affected by the presence or absence of carbon. Molybdenum isotope fractionation is furthermore independent of oxygen fugacity in the range IW -1.79 to IW +0.47, which are plausible values for core formation. Experiments at 1600 °C show that, at equilibrium, the 98Mo/95Mo ratio of silicate is 0.12±0.02‰ heavier than that of metal and that the presence or absence of Sn does not affect this fractionation. Equilibrium Mo isotope fractionation between liquid metal and liquid silicate as a function of temperature can therefore be described as ΔMoMetal-Silicate98/95=-4.70(±0.59)×105/T2. Our experiments show that Mo isotope fractionation may be resolvable up to metal-silicate equilibration temperatures of about 2500 °C, rendering Mo isotopes a novel tool to investigate the conditions of core formation in objects ranging from planetesimals to Earth sized bodies.

  11. The importance of the Maillard-metal complexes and their silicates in astrobiology

    NASA Astrophysics Data System (ADS)

    Liesch, Patrick J.; Kolb, Vera M.

    2007-09-01

    The Maillard reaction occurs when sugars and amino acids are mixed together in the solid state or in the aqueous solution. Since both amino acids and sugar-like compounds are found on meteorites, we hypothesized that they would also undergo the Maillard reaction. Our recent work supports this idea. We have shown previously that the water-insoluble Maillard products have substantial similarities with the insoluble organic materials from the meteorites. The Maillard organic materials are also part of the desert varnish on Earth, which is a dark, shiny, hard rock coating that contains iron and manganese and is glazed in silicate. Rocks that are similar in appearance to the desert varnish have been observed on the Martian surface. They may also contain the organic materials. We have undertaken study of the interactions between the Maillard products, iron and other metals, and silicates, to elucidate the role of the Maillard products in the chemistry of desert varnish and meteorites. Specifically, we have synthesized a series of the Maillard-metal complexes, and have tested their reactivity towards silicates. We have studied the properties of these Maillard-metal-silicate products by the IR spectroscopy. The astrobiological potential of the Maillard-metal complexes is assessed.

  12. High Temperature Effects on Pt Partitioning Between Metal and Mafic Silicate Liquids: Implications for Core Formation

    NASA Astrophysics Data System (ADS)

    Cottrell, E.; Walker, D.

    2005-12-01

    A new high temperature piston cylinder design has enabled the measurement of platinum solubility in mafic melts at temperatures up to to 2500°C, 2.2GPa pressure, and under reducing conditions for 1 - 10 hours. These high temperatures and low fO2 conditions may mimic a magma ocean during planetary core formation. Under these conditions, we measured tens to hundreds of ppm Pt in the quenched silicate glass corresponding to DPtmetal/silicate ~ 103-4, 4 to 12 orders of magnitude lower than extrapolations from high fO2 experiments at 1 bar and at temperatures no higher than 1550°C. Moreover, the new experiments provide strong evidence that noble metal micronuggets, ubiquitous in experimental studies of the HSE, can be produced on quench. We measure equally high Pt concentrations in nugget-bearing and nugget-free regions of the quenched silicate, consistent with the quench interpretation. We find that both temperature and melt composition exercise strong control on DPtmetal/silicate and that Pt0 and Pt+1 may contribute significantly to the total dissolved Pt such that low fO2 does not imply low Pt solubility. Equilibration of metal alloy with liquid silicate in a hot primitive magma might not have depleted platinum to the extent previously believed.

  13. Experimentally determined sulfur isotope fractionation between metal and silicate and implications for planetary differentiation

    NASA Astrophysics Data System (ADS)

    Labidi, J.; Shahar, A.; Le Losq, C.; Hillgren, V. J.; Mysen, B. O.; Farquhar, J.

    2016-02-01

    The Earth's mantle displays a subchondritic 34S/32S ratio. Sulfur is a moderately siderophile element (i.e. iron-loving), and its partitioning into the Earth's core may have left such a distinctive isotope composition on the terrestrial mantle. In order to constrain the sulfur isotope fractionation occurring during core-mantle differentiation, high-pressure and temperature experiments were conducted with synthetic mixtures of metal and silicate melts. With the purpose to identify the mechanism(s) responsible for the S isotope fractionations, we performed our experiments in different capsules - namely, graphite and boron nitride capsules - and thus at different fO2, with varying major element chemistry of the silicate and metal fractions. The S isotope fractionations Δ34Smetal-silicate of equilibrated metal alloys versus silicate melts is +0.2 ± 0.1‰ in a boron-free and aluminum-poor system quenched at 1-1.5 GPa and 1650 °C. The isotope fractionation increases linearly with increasing boron and aluminum content, up to +1.4 ± 0.2‰, and is observed to be independent of the silicon abundance as well as of the fO2 over ∼3.5 log units of variations explored here. The isotope fractionations are also independent of the graphite or nitride saturation of the metal. Only the melt structural changes associated with aluminum and boron concentration in silicate melts have been observed to affect the strength of sulfur bonding. These results establish that the structure of silicate melts has a direct influence on the S2- average bonding strengths. These results can be interpreted in the context of planetary differentiation. Indeed, the structural environments of silicate evolve strongly with pressure. For example, the aluminum, iron or silicon coordination numbers increase under the effect of pressure. Consequently, based on our observations, the sulfur-bonding environment is likely to be affected. In this scheme, we tentatively hypothesize that S isotope fractionations

  14. 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.

  15. 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.

  16. Alkali metal mediated C-C bond coupling reaction

    NASA Astrophysics Data System (ADS)

    Tachikawa, Hiroto

    2015-02-01

    Metal catalyzed carbon-carbon (C-C) bond formation is one of the important reactions in pharmacy and in organic chemistry. In the present study, the electron and hole capture dynamics of a lithium-benzene sandwich complex, expressed by Li(Bz)2, have been investigated by means of direct ab-initio molecular dynamics method. Following the electron capture of Li(Bz)2, the structure of [Li(Bz)2]- was drastically changed: Bz-Bz parallel form was rapidly fluctuated as a function of time, and a new C-C single bond was formed in the C1-C1' position of Bz-Bz interaction system. In the hole capture, the intermolecular vibration between Bz-Bz rings was only enhanced. The mechanism of C-C bond formation in the electron capture was discussed on the basis of theoretical results.

  17. Alkali metal mediated C–C bond coupling reaction

    SciTech Connect

    Tachikawa, Hiroto

    2015-02-14

    Metal catalyzed carbon-carbon (C–C) bond formation is one of the important reactions in pharmacy and in organic chemistry. In the present study, the electron and hole capture dynamics of a lithium-benzene sandwich complex, expressed by Li(Bz){sub 2}, have been investigated by means of direct ab-initio molecular dynamics method. Following the electron capture of Li(Bz){sub 2}, the structure of [Li(Bz){sub 2}]{sup −} was drastically changed: Bz–Bz parallel form was rapidly fluctuated as a function of time, and a new C–C single bond was formed in the C{sub 1}–C{sub 1}′ position of Bz–Bz interaction system. In the hole capture, the intermolecular vibration between Bz–Bz rings was only enhanced. The mechanism of C–C bond formation in the electron capture was discussed on the basis of theoretical results.

  18. Nanotubes within transition metal silicate hollow spheres: Facile preparation and superior lithium storage performances

    SciTech Connect

    Zhang, Fan; An, Yongling; Zhai, Wei; Gao, Xueping; Feng, Jinkui; Ci, Lijie; Xiong, Shenglin

    2015-10-15

    Highlights: • The hollow Co{sub 2}SiO{sub 4}, MnSiO{sub 3} and CuSiO{sub 3} were successfully prepared by a facile hydrothermal method using SiO{sub 2} nanosphere. • The hollow Co{sub 2}SiO{sub 4}, MnSiO{sub 3} and CuSiO{sub 3} were tested as anode materials for lithium batteries. • The hollow Co{sub 2}SiO{sub 4}, MnSiO{sub 3} and CuSiO{sub 3} delivered superior electrochemical performance. • The lithium storage mechanism is probe via cyclic voltammetry and XPS. - Abstract: A series of transition metal silicate hollow spheres, including cobalt silicate (Co{sub 2}SiO{sub 4}), manganese silicate (MnSiO{sub 3}) and copper silicate (CuSiO{sub 3}.2H{sub 2}O, CuSiO{sub 3} as abbreviation in the text) were prepared via a simple and economic hydrothermal method by using silica spheres as chemical template. Time-dependent experiments confirmed that the resultants formed a novel type of hierarchical structure, hollow spheres assembled by numerous one-dimensional (1D) nanotubes building blocks. For the first time, the transition metal silicate hollow spheres were characterized as novel anode materials of Li-ion battery, which presented superior lithium storage capacities, cycle performance and rate performance. The 1D nanotubes assembly and hollow interior endow this kind of material facilitate fast lithium ion and electron transport and accommodate the big volume change during the conversion reactions. Our study shows that low-cost transition metal silicate with rationally designed nanostructures can be promising anode materials for high capacity lithium-ion battery.

  19. Post-Harvest Processing Methods for Reduction of Silica and Alkali Metals in Wheat Straw

    SciTech Connect

    Thompson, David Neal; Lacey, Jeffrey Alan; Shaw, Peter Gordon

    2002-04-01

    Silica and alkali metals in wheat straw limit its use for bioenergy and gasification. Slag deposits occur via the eutectic melting of SiO2 with K2O, trapping chlorides at surfaces and causing corrosion. A minimum melting point of 950°C is desirable, corresponding to SiO2:K2O of about 3:1. Mild chemical treatments were used to reduce Si, K, and Cl, while varying temperature, concentration, %-solids, and time. Dilute acid was more effective at removing K and Cl, while dilute alkali was more effective for Si. Reduction of minerals in this manner may prove economical for increasing utilization of the straw for combustion or gasification.

  20. Thermometry of the magma ocean: Controls on the metal-silicate partitioning of gold

    NASA Astrophysics Data System (ADS)

    Bennett, N. R.; Brenan, J. M.; Fei, Y.

    2016-07-01

    We have performed experiments to investigate the solubility and metal-silicate partitioning of gold as a function of metal sulphur content (XS), silicate melt polymerization (NBO/T) and pressure (P). These experiments show that Au becomes less siderophile both with increasing pressure and as the metal phase becomes more sulphur-rich. For the studied range of compositions, melt polymerization has no effect on the solubility of Au. The reduction in the siderophile tendency of gold with increasing metal sulphur content is greater than expected on the basis of activity-composition relationships in the metal phase. This suggests a significant role for complexing between Au and S in the silicate melt. Our new experimental results are combined with literature data to yield a parameterisation for the exchange coefficient of Au (KdAuMet/Sil) as a function of P, T and XS: Using this relationship, alongside similar parameterisations for Ni and Co selected from the literature, we performed continuous accretion models to delineate regions of parameter space in which Au and moderately siderophile element (MSE) abundances in the primitive upper mantle (PUM) could be reproduced. These models suggest that for metal-silicate equilibrium at very high pressures, Au will be overabundant in the PUM if equilibrium also occurs at extreme temperatures. Instead, most successful models are found when equilibrium occurs at high pressure but sub-liquidus temperatures. This result is in keeping with the physical conditions expected for a scenario where core-forming metal ponds and equilibrates at the rheological base of a magma ocean (e.g. Wade and Wood, 2005).

  1. Influence of alkaline earth metals on molecular structure of 3-nitrobenzoic acid in comparison with alkali metals effect

    NASA Astrophysics Data System (ADS)

    Samsonowicz, M.; Regulska, E.; Lewandowski, W.

    2011-11-01

    The influence of beryllium, magnesium, calcium, strontium and barium cations on the electronic system of 3-nitrobenzoic acid was studied in comparison with studied earlier alkali metal ions [1]. The vibrational FT-IR (in KBr and ATR techniques) and 1H and 13C NMR spectra were recorded for 3-nitrobenzoic acid and its salts. Characteristic shifts in IR and NMR spectra along 3-nitrobenzoates of divalent metal series Mg → Ba were compared with series of univalent metal Li → Cs salts. Good correlations between the wavenumbers of the vibrational bands in the IR spectra for 3-nitrobenzoates and ionic potential, electronegativity, inverse of atomic mass, atomic radius and ionization energy of metals were found for alkaline earth metals as well as for alkali metals. The density functional (DFT) hybrid method B3LYP with two basis sets: 6-311++G** and LANL2DZ were used to calculate optimized geometrical structures of studied compounds. The theoretical wavenumbers and intensities of IR spectra as well as chemical shifts in NMR spectra were obtained. Geometric aromaticity indices, atomic charges, dipole moments and energies were also calculated. The calculated parameters were compared to experimental characteristic of studied compounds.

  2. Kinetics of iron redox reaction in silicate melts: A high temperature Xanes study on an alkali basalt

    NASA Astrophysics Data System (ADS)

    Cochain, B.; Neuville, D. R.; de Ligny, D.; Roux, J.; Baudelet, F.; Strukelj, E.; Richet, P.

    2009-11-01

    In Earth and Materials sciences, iron is the most important transition element. Glass and melt properties are strongly affected by iron content and redox state with the consequence that some properties (i.e. viscosity, heat capacity, crystallization...) depend not only on the amounts of Fe2+ and Fe3+, but also on the coordination state of these ions. In this work we investigate iron redox reactions through XANES experiments at the K-edge of iron. Using a high-temperature heating device, pre-edge of XANES spectra exhibits definite advantages to make in-situ measurements and to determine the evolution of redox state with time, temperature and composition of synthetic silicate melts. In this study, new kinetics measurements are presented for a basalt melt from the 31,000-BC eruption of the Puy de Lemptegy Volcano in France. These measurements have been made between 773 K and at superliquidus temperatures up to 1923 K.

  3. Experimentally determined Si isotope fractionation between silicate and Fe metal and implications for Earth's core formation

    NASA Astrophysics Data System (ADS)

    Shahar, Anat; Ziegler, Karen; Young, Edward D.; Ricolleau, Angele; Schauble, Edwin A.; Fei, Yingwei

    2009-10-01

    Stable isotope fractionation amongst phases comprising terrestrial planets and asteroids can be used to elucidate planet-forming processes. To date, the composition of the Earth's core remains largely unknown though cosmochemical and geophysical evidence indicates that elements lighter than iron and nickel must reside there. Silicon is often cited as a light element that could explain the seismic properties of the core. The amount of silicon in the core, if any, can be deduced from the difference in 30Si/ 28Si between meteorites and terrestrial rocks if the Si isotope fractionation between silicate and Fe-rich metal is known. Recent studies (e.g., [Georg R.B., Halliday A.N., Schauble E.A., Reynolds B.C., 2007. Silicon in the Earth's core. Nature 447 (31), 1102-1106.]; [Fitoussi, C., Bourdon, B., Kleine, T., Oberli, F., Reynolds, B. C., 2009. Si isotope systematics of meteorites and terrestrial peridotites: implications for Mg/Si fractionation in the solar nebula and for Si in the Earth's core. Earth Planet. Sci. Lett. 287, 77-85.]) showing (sometimes subtle) differences between 30Si/ 28Si in meteorites and terrestrial rocks suggest that Si missing from terrestrial rocks might be in the core. However, any conclusion based on Earth-meteorite comparisons depends on the veracity of the 30Si/ 28Si fractionation factor between silicates and metals at appropriate conditions. Here we present the first direct experimental evidence that silicon isotopes are not distributed uniformly between iron metal and rock when equilibrated at high temperatures. High-precision measurements of the silicon isotope ratios in iron-silicon alloy and silicate equilibrated at 1 GPa and 1800 °C show that Si in silicate has higher 30Si/ 28Si than Si in metal, by at least 2.0‰. These findings provide an experimental foundation for using isotope ratios of silicon as indicators of terrestrial planet formation processes. They imply that if Si isotope equilibrium existed during segregation of Earth

  4. Building a Chemical Intuition Under Pressure: Prediction of Alkali Metal Polyhydrides and Subhydrides

    NASA Astrophysics Data System (ADS)

    Zurek, Eva

    2013-06-01

    Stabilization of solid phases with unusual combinations or stoichiometries, and unexpected electronic structures may be achieved by applying external pressure. The prediction of these structures using our chemical intuition (developed at 1 atmosphere) would be exceedingly difficult, making automated structure search techniques prudent. For this reason, we have written XtalOpt, an open-source evolutionary algorithm for crystal structure prediction. Whereas at 1 atmosphere the classic alkali hydrides combine in a one-to-one ratio, M+H-, under pressure non-classic stoichiometries MHn(n > 1) and MmH (m > 1) are preferred. For example, theoretical work has predicted that LiH6 and NaH9 become particularly stable phases at about 100 and 25 GPa, respectively. And the potassium, rubidium and cesium polyhydrides all contain the H3-anion, the simplest exaple of a three centered four electron bond. The alkaline-earth polyhydrides are considered as well. Chemical trends relating the stabilization pressure to the ionization potential, and the nature of the hydrogenic sublattice to the strength of the metal-hydride interaction can be made. These hydrogen-rich materials with nontraditional stoichiometries are computed to undergo an insulator to metal transition at pressures attainable in diamond anvil cells. It may be that these systems are superconductors at experimentally achievable pressures. The metal-rich region of the alkali/hydrogen phase diagram under pressure shows that alkali-metal subhydrides may also be stabilized under pressure. We acknowledge the NSF (DMR-1005413) for financial support.

  5. Subtask 12E1: Compatibility of structural materials in liquid alkali metals

    SciTech Connect

    Natesan, K.; Rink, D.L.; Haglund, R.; Clark, R.W.

    1995-03-01

    The objectives of this task are to (a) evaluate the chemical compatibility of structural alloys such as V-5 wt.%Cr-5 wt.%Ti alloy and Type 316 stainless steel for application in liquid alkali metals such as lithium and sodium-78 wt.% potassium (NaK) at temperatures that are in the range of interest for the International Thermonuclear Experimental Reactor (ITER); (b) evaluate the transfer of nonmetallic elements such as oxygen, nitrogen, carbon, and hydrogen between structural materials and liquid metals; and (c) evaluate the effects of such transfers on the mechanical and microstructural characteristics of the materials for long-term service in liquid-metal environments. Candidate structural materials are being evaluated for their compatibility, interstitial-element transfer, and corrosion in liquid alkali-metal systems such as lithium and NaK. Type 316 stainless steel and V-5Cr-5Ti coupon specimens with and without prealuminizing treatment have been exposed to NaK and lithium environments of commercial purity for times up to 3768 h at temperatures between 300 and 400{degrees}C. 13 refs., 8 figs., 3 tabs.

  6. Alkali Metal Based Micro Combustion Using Graphene Micro-valve Trigger

    NASA Astrophysics Data System (ADS)

    Ruyack, A.; Gund, V.; Camera, K.; Ardanuç, S.; Ober, C.; Lal, A.

    2015-12-01

    Controllable combustion of alkali metals offers a pathway to high energy density, high power density scalable thermal systems. The volatile nature of these materials however, has limited their incorporation into useable devices. Recent findings in low trigger power MEMS one-shot valves offer a viable pathway forward for creating systems in which to exploit the unique properties of alkali metals as thermal energy sources. By miniaturizing and combining these fuels with such a valve, and incorporating them with a polymer substrate, a micro-packet of combustible metal can be created. Here we report such a device utilizing a graphene based micro-valve trigger and a rubidium metal fuel source to realize an arrayable micro-scale electrical to thermal energy amplification scheme. Using this approach we can react nanoliter droplets of rubidium with ambient air on demand, producing electrical to thermal energy gains of seventy five times. By arraying the fuel into discrete packets, we can also achieve temporal control of the fuel source, allowing for tailored peak and average power output.

  7. The role of alkalis in the solubility of H2O and CO2in silicate melts

    NASA Astrophysics Data System (ADS)

    Vetere, F.; Behrens, H.; Botcharnikov, R. E.; Holtz, F.; Fanara, S.

    2013-12-01

    In order to investigate the role of alkalis on the behavior of H2O and CO2 in magmatic systems, the solubility of volatiles in phonotephritic melts was investigated experimentally and compared to other melt compositions. The investigated compositions have Na2O/K2O ratios (in wt %) of 0.26 (Ab1, natural phonotephrite from Alban Hills, Italy), 0.98 (Ab2) and 3.82 (Ab3). Experiments were run at 1250°C and 500 MPa in an internally heated gas pressure vessel. The mole fraction of water (XH2O) in the fluid phase composed of H2O and CO2 varied in the range from 0 to 1. For the calibration of carbon-related IR bands in glasses, the total carbon content of synthesized glass standards was measured by combustion and subsequent IR spectroscopy using an ELTRA CS800 analyzer. Karl Fischer Titration method was used to quantify the H2O content of the glasses. Absorption spectra were recorded in the mid-infrared (MIR) using a Bruker IFS88 FTIR spectrometer coupled with an IR-ScopeII microscope. CO2 is bounded in the investigated glasses as CO32- exclusively and its concentration was quantified by the peak height of the 1430 cm-1 band. A drastic change was observed in the absorption coefficients, ɛ, with values of 294 × 35, 329 × 40 and 244 × 23 L/(mol cm) , for Ab1, Ab2, and Ab3, respectively, so that the highest ɛ value is related to the Na-rich composition. There is no evident effect of the Na/K ratio on the concentrations of dissolved H2O and CO2 in the melts. The solubility of CO2 and H2O in those melts at 500 MPa is 0.95 wt % CO2 and 10.07 wt% H2O for XH2O of 0 and 1, respectively. Results are compared with the existing literature data and models and confirm the very high solubility of CO2 in phonotephritic melts [1]. Our experimental data indicate that the melt composition in terms of alkali contents influences significantly the extinction coefficient values for CO2 and that appropriate coefficients must be selected to estimate accurately the amount of dissolved CO2 in

  8. Modification of conductive properties of (10, 0) zigzag single-walled carbon nanotubes (SWCNT) by alkali metals absorption

    NASA Astrophysics Data System (ADS)

    Hamadanian, Masood; Tavangar, Zahra; Noori, Banafsheh

    2014-11-01

    We have investigated the electronic and structural properties of (10, 0) zigzag single-walled carbon nanotubes (SWCNT) which have adsorbed different alkali metals (X: Li, Na, K, and Cs) and the hydrogen atom by using Density Functional Theory (DFT). It was discovered that among the alkali elements, Li atoms form the strongest bond with SWCNT. In addition, a significant shift was observed in the electronic state of alkali-adsorbed SWCNT compared to pristine SWCNT. Finally, it was proposed that due to showing excellent electronic structure, these modified nanotubes can be applied in new electronic devices, such as transistors, and field emission displays.

  9. Gallium and germanium in the metal and silicates of L- and LL-chondrites.

    NASA Technical Reports Server (NTRS)

    Chou, C.-L.; Cohen, A. J.

    1973-01-01

    Concentrations of Ga and Ge in the metal of 31 L-, 8 LL- and 2 H-chondrites, and in the silicates of 12 L- and LL-chondrites have been determined by spectrophotometric methods. The ranges of Ga contents in the metal of L- and LL-chondrites are 1.1 to 36.9 ppm and 1.0 to 34.1 ppm, respectively. The Ge content in the metal is positively correlated with Ga and ranges from 89.1 to 160 ppm and from 126 to 308 ppm for L- and LL-chondrites, respectively. The Ga content in the silicates of L-chondrites varies from 4.0 to 8.9 ppm. The Ga and Ge contents in the metal are clearly lower in unequilibrated than in equilibrated L- and LL-group chondrites. Unequilibrated and equilibrated chondrites are well separated in the plots of Ga vs Ge in the metal, and the L- and LL-groups are also well resolved. The Ga and Ge in the metal are well correlated with petrologic grade. This suggests that Ga and Ge variations in the metal are related to thermal metamorphism. There is evidence of an enrichment of Ga in the metal due to shock reheating.

  10. Metal/Silicate Partitioning, Melt Speciation, Accretion, and Core Formation in the Earth

    NASA Astrophysics Data System (ADS)

    Drake, M. J.; Hillgren, V. J.; Dearo, J. A.; Capobianco, C. J.

    1993-07-01

    Core formation in terrestrial planets was concomitant with accretion. Siderophile and chalcophile element signatures in the mantles of planets are the result of these processes. For Earth, abundances of most siderophile and chalcophile elements are elevated relative to predictions from simple metal/silicate equilibria at low pressures [1]. This observation has led to three hypotheses for how these abundances were established: heterogeneous accretion [2], inefficient core formation [3], and metal/silicate equilibria at magma ocean pressures and temperatures [4]. Knowledge of speciation of siderophile elements in silicate melts in equilibrium with metal may help distinguish between these hypotheses. But there is some uncertainty regarding speciation. For example, Ni and Co have been reported to be present as 1+ or zero valence species in silicate melts at redox states appropriate to planetary accretion, rather than the expected 2+ state [5-7]. Independent metal/silicate partitioning experiments by three members of this group using two different experimental designs on both synthetic and natural compositions do not show evidence for Ni and Co in valence states other than 2+ over a wide range of redox states. For example, solid metal/silicate melt partition coefficients for Ni at 1260 degrees C obtained by VJH from experiments investigating the partitioning of Ni, Co, Mo, W, and P are indistinguishable from those obtained by JAD in similar experiments investigating the partitioning of Ni, Ge, and Sn. Both datasets define a line with the equation: log D(Ni) = - 0.54log fO2 - 3.14 with r^2 > 0.995. (Note that fO2 was calculated in both studies from thermodynamic data and phase compositions. A small, systematic offset from the true fO2 as measured by a solid electrolyte cell affects both equations similarly, but does not diminish their close agreement.) The valence of Ni in the silicate melt is obtained by multiplying the slope of the line by -4, indicating divalent Ni in

  11. Binding of monovalent alkali metal ions with negatively charged phospholipid membranes.

    PubMed

    Maity, Pabitra; Saha, Baishakhi; Kumar, Gopinatha Suresh; Karmakar, Sanat

    2016-04-01

    We have systematically investigated the effect of various alkali metal ions with negatively charged phospholipid membranes. Size distributions of large unilamellar vesicles have been confirmed using dynamic light scattering. Zeta potential and effective charges per vesicle in the presence of various alkali metal ions have been estimated from the measured electrophoretic mobility. We have determined the intrinsic binding constant from the zeta potential using electrostatic double layer theory. The reasonable and consistent value of the intrinsic binding constant of Na(+), found at moderate NaCl concentration (10-100 mM), indicates that the Gouy-Chapman theory cannot be applied for very high (> 100mM) and very low (< 10 mM) electrolyte concentrations. The isothermal titration calorimetry study has revealed that the net binding heat of interaction of the negatively charged vesicles with monovalent alkali metal ions is small and comparable to those obtained from neutral phosphatidylcholine vesicles. The overall endothermic response of binding heat suggests that interaction is primarily entropy driven. The entropy gain might arise due to the release of water molecules from the hydration layer vicinity of the membranes. Therefore, the partition model which does not include the electrostatic contribution suffices to describe the interaction. The binding constant of Na(+) (2.4 ± 0.1 M(-1)), obtained from the ITC, is in agreement with that estimated from the zeta potential (-2.0 M(-1)) at moderate salt concentrations. Our results suggest that hydration dynamics may play a vital role in the membrane solution interface which strongly affects the ion-membrane interaction. PMID:26802251

  12. Condensates from vapor made by impacts between metal-, silicate-rich bodies: Comparison with metal and chondrules in CB chondrites

    NASA Astrophysics Data System (ADS)

    Fedkin, Alexei V.; Grossman, Lawrence; Humayun, Munir; Simon, Steven B.; Campbell, Andrew J.

    2015-09-01

    The impact hypothesis for the origin of CB chondrites was tested by performing equilibrium condensation calculations in systems composed of vaporized mixtures of projectile and target materials. When one of the impacting bodies is composed of the metal from CR chondrites and the other is an H chondrite, good agreement can be found between calculated and observed compositions of unzoned metal grains in CB chondrites but the path of composition variation of the silicate condensate computed for the same conditions that reproduce the metal grain compositions does not pass through the measured compositions of barred olivine (BO) or cryptocrystalline (CC) chondrules in the CBs. The discrepancy between measured chondrule compositions and those of calculated silicates is not reduced when diogenite, eucrite or howardite compositions are substituted for H chondrite as the silicate-rich impacting body. If, however, a CR chondrite body is differentiated into core, a relatively CaO-, Al2O3-poor mantle and a CaO-, Al2O3-rich crust, and later accretes significant amounts of water, a collision between it and an identical body can produce the necessary chemical conditions for condensation of CB chondrules. If the resulting impact plume is spatially heterogeneous in its proportions of crust and mantle components, the composition paths calculated for silicate condensates at the same Ptot, Ni/H and Si/H ratios and water abundance that produce good matches to the unzoned metal grain compositions pass through the fields of BO and CC chondrules, especially if high-temperature condensates are fractionated in the case of the CCs. While equilibrium evaporation of an alloy containing solar proportions of siderophiles into a dense impact plume is an equally plausible hypothesis for explaining the compositions of the unzoned metal grains, equilibrium evaporation can explain CB chondrule compositions only if an implausibly large number of starting compositions is postulated. Kinetic models

  13. Thermal and chemical diffusion within conduits of sinking metal-silicate plumes during core formation events.

    NASA Astrophysics Data System (ADS)

    Weeraratne, D. S.; Olson, P. L.

    2008-12-01

    Early and rapid core formation is suggested by recent isotopic studies. Accumulation of a short lived liquid metal pond at the base of a magma ocean during early impacts may provide a model for chemical diffusion of silicates and liquid metal to produce the observed abundances of siderophile elements in the Earth's mantle. Here we present results from laboratory fluid experiments of liquid gallium in high viscosity stratified corn syrup solutions to model the physical dynamics of core formation processes in the early Earth. Experiments are designed to consider the instability of a dense liquid metal pond as single droplets, Rayleigh-Taylor instability, and evolution of a liquid metal emulsion layer. We find that in all cases, a wide trailing conduit develops behind rapidly descending metallic plumes which entrains low density fluid to the base of the fluid box. We propose a model where the conduit itself provides a vehicle for thermal and chemical equilibration between metals and silicates at high pressures and temperatures during its path through the lower mantle. Diffusion processes contribute to the formation of this new entrained fluid layer at the base of the fluid box which is buoyant and evolves into a new type of thermo-chemical plume which subsequently rises. Using a range of viscosity and buoyancy ratios, experimental results will constrain the time scales for instability of a liquid metal pond, descent and upwelling times of this unique type of plume, as well as the nature and dynamics of conduit formation. This model provides a high pressure/temperature environment for metal- silicate equilibration consistent with petrologic and isotopic studies, is consistent with rapid core formation, and may also connect core formation to ancient hotspot activity on terrestrial planets.

  14. Intercalation of heavy alkali metals (K, Rb and Cs) in the bundles of single wall nanotubes

    NASA Astrophysics Data System (ADS)

    Duclaux, L.; Méténier, K.; Lauginie, P.; Salvetat, J. P.; Bonnamy, S.; Beguin, F.

    2000-11-01

    The electric-arc discharge carbon deposits (collaret) containing Single Wall Carbon Nanotubes (SWNTs) were heat treated at 1600 °C during 2 days under N2 flow in order to eliminate the Ni catalyst by sublimation, without modifications of the SWNTs ropes. Sorting this deposit by gravity enabled to obtain in the coarsest particles higher amount of SWNTs ropes than in other particle sizes. The coarser particles of the carbon deposits were reacted with the alkali metals vapor giving intercalated samples with a MC8 composition. The intercalation led to an expansion of the 2D lattice of the SWNTs so that the alkali metals were intercalated in between the tubes within the bundles. Disordered lattices were observed after intercalation of Rb and Cs. The simulations of the X-ray diffractograms of SWNTs reacted with K, gave the best fit for three K ions occupying the inter-tubes triangular cavities. The investigations by EPR, and 13C NMR, showed that doped carbon deposits are metallic.

  15. Metal Hydride and Alkali Halide Opacities in Extrasolar Giant Planets and Cool Stellar Atmospheres

    NASA Technical Reports Server (NTRS)

    Weck, Philippe F.; Stancil, Phillip C.; Kirby, Kate; Schweitzer, Andreas; Hauschildt, Peter H.

    2006-01-01

    The lack of accurate and complete molecular line and continuum opacity data has been a serious limitation to developing atmospheric models of cool stars and Extrasolar Giant Planets (EGPs). We report our recent calculations of molecular opacities resulting from the presence of metal hydrides and alkali halides. The resulting data have been included in the PHOENIX stellar atmosphere code (Hauschildt & Baron 1999). The new models, calculated using spherical geometry for all gravities considered, also incorporate our latest database of nearly 670 million molecular lines, and updated equations of state.

  16. High power density performance of WPt and WRh electrodes in the alkali metal thermoelectric converter

    NASA Technical Reports Server (NTRS)

    Williams, R. M.; Jeffries-Nakamura, B.; Underwood, M. L.; Wheeler, B. L.; Loveland, M. E.; Kikkert, S. J.; Lamb, J. L.; Cole, T.; Kummer, J. T.; Bankston, C. P.

    1989-01-01

    The properties of the alkali metal thermoelectric converter (AMTEC) are discussed together with those of an efficient AMTEC electrode. Three groups of electrodes were prepared and tested for their performance as AMTEC electrodes, including WPt-T3, WRh-B1, and WRh-B2. The best electrodes of both WPt and WRh types typically exhibited low porosity, and thickness greater than 0.8 micron, which indicated that transport in these electrodes does not occur by a purely free-molecular flow mode. The observed values of the exchange current were found to be within the range of those observed for oxide-free Mo electrodes under similar conditions.

  17. Threshold behavior of positronium formation in positron-alkali-metal scattering

    NASA Astrophysics Data System (ADS)

    Lugovskoy, A. V.; Utamuratov, R.; Kadyrov, A. S.; Stelbovics, A. T.; Bray, I.

    2013-04-01

    We consider positron scattering on the alkali-metal atoms of Li, Na, and K at very low energies, where only the elastic scattering and positronium formation in the ground state are the two open channels. Utilizing the recently developed two-center convergent close-coupling method [Lugovskoy, Kadyrov, Bray, and Stelbovics, Phys. Rev. APLRAAN1050-294710.1103/PhysRevA.82.062708 82, 062708 (2010)] we investigate the behavior of the cross sections as the impact energy goes to zero and demonstrate their convergence. The study sets quantitative benchmarks for any rigorous theoretical treatment of the collision problems.

  18. Positron binding to alkali-metal hydrides: The role of molecular vibrations

    NASA Astrophysics Data System (ADS)

    Gianturco, Franco A.; Franz, Jan; Buenker, Robert J.; Liebermann, Heinz-Peter; Pichl, Lukáš; Rost, Jan-Michael; Tachikawa, Masanori; Kimura, Mineo

    2006-02-01

    The bound vibrational levels for J=0 have been computed for the series of alkali-metal hydride molecules from LiH to RbH, including NaH and KH. For all four molecules the corresponding potential-energy curves have been obtained for each isolated species and for its positron-bound complex (e+XH) . It is found that the calculated positron affinity values strongly depend on the molecular vibrational state for which they are obtained and invariably increase as the molecular vibrational energy content increases. The consequences of our findings on the likelihood of possibly detecting such weakly bound species are briefly discussed.

  19. Calculating the thermodynamic properties of aqueous solutions of alkali metal carboxylates

    NASA Astrophysics Data System (ADS)

    Rudakov, A. M.; Sergievskii, V. V.; Zhukova, T. V.

    2014-06-01

    A modified Robinson-Stokes equation with terms that consider the formation of ionic hydrates and associates is used to describe thermodynamic properties of aqueous solutions of electrolytes. The model is used to describe data on the osmotic coefficients of aqueous solutions of alkali metal carboxylates, and to calculate the mean ionic activity coefficients of salts and excess Gibbs energies. The key contributions from ionic hydration and association to the nonideality of solutions is determined by analyzing the contributions of various factors. Relations that connect the hydration numbers of electrolytes with the parameters of the Pitzer-Mayorga equation and a modified Hückel equation are developed.

  20. Alkali-metal gases in optical lattices: Possible new type of quantum crystals

    NASA Astrophysics Data System (ADS)

    Meyerovich, A. E.

    2003-11-01

    Similarities between alkali-metal gases in optical lattices with noninteger occupation of the lattice sites and quantum crystals are explored. The analogy with the vacancy liquid (VL) provides an alternative explanation to the Mott transition for the recent experiment on the phase transition in the lattice. The VL can undergo Bose-Einstein condensation (BEC) with Tc within experimental reach. Direct and vacancy-assisted mechanisms of the band motion for hyperfine impurities are discussed. A large concentration of vacancies can result in the spatial decomposition of the system into pure hyperfine components. Below the vacancy condensation the impurity component resembles 3He in 3He He II mixtures.

  1. PHOTOPHORETIC SEPARATION OF METALS AND SILICATES: THE FORMATION OF MERCURY-LIKE PLANETS AND METAL DEPLETION IN CHONDRITES

    SciTech Connect

    Wurm, Gerhard; Trieloff, Mario; Rauer, Heike

    2013-05-20

    Mercury's high uncompressed mass density suggests that the planet is largely composed of iron, either bound within metal (mainly Fe-Ni) or iron sulfide. Recent results from the MESSENGER mission to Mercury imply a low temperature history of the planet which questions the standard formation models of impact mantle stripping or evaporation to explain the high metal content. Like Mercury, the two smallest extrasolar rocky planets with mass and size determination, CoRoT-7b and Kepler-10b, were found to be of high density. As they orbit close to their host stars, this indicates that iron-rich inner planets might not be a nuisance of the solar system but be part of a general scheme of planet formation. From undifferentiated chondrites, it is also known that the metal to silicate ratio is highly variable, which must be ascribed to preplanetary fractionation processes. Due to this fractionation, most chondritic parent bodies-most of them originated in the asteroid belt-are depleted in iron relative to average solar system abundances. The astrophysical processes leading to metal silicate fractionation in the solar nebula are essentially unknown. Here, we consider photophoretic forces. As these forces particularly act on irradiated solids, they might play a significant role in the composition of planetesimals forming at the inner edge of protoplanetary disks. Photophoresis can separate high thermal conductivity materials (iron) from lower thermal conductivity solids (silicate). We suggest that the silicates are preferentially pushed into the optically thick disk. Subsequent planetesimal formation at the edge moving outward leads to metal-rich planetesimals close to the star and metal depleted planetesimals farther out in the nebula.

  2. Carboxylate Ion Pairing with Alkali-Metal Ions for β-Lactoglobulin and Its Role on Aggregation and Interfacial Adsorption.

    PubMed

    Beierlein, Frank R; Clark, Timothy; Braunschweig, Björn; Engelhardt, Kathrin; Glas, Lena; Peukert, Wolfgang

    2015-04-30

    We report a combined experimental and computational study of the whey protein β-lactoglobulin (BLG) in different electrolyte solutions. Vibrational sum-frequency generation (SFG) and ellipsometry were used to investigate the molecular structure of BLG modified air-water interfaces as a function of LiCl, NaCl, and KCl concentrations. Molecular dynamics (MD) simulations and thermodynamic integration provided details of the ion pairing of protein surface residues with alkali-metal cations. Our results at pH 6.2 indicate that BLG at the air-water interface forms mono- and bilayers preferably at low and high ionic strength, respectively. Results from SFG spectroscopy and ellipsometry are consistent with intimate ion pairing of alkali-metal cations with aspartate and glutamate carboxylates, which is shown to be more effective for smaller cations (Li(+) and Na(+)). MD simulations show not only carboxylate-alkali-metal ion pairs but also ion multiplets with the alkali-metal ion in a bridging position between two or more carboxylates. Consequently, alkali-metal cations can bridge carboxylates not only within a monomer but also between monomers, thus providing an important dimerization mechanism between hydrophilic surface patches. PMID:25825918

  3. Accretion and core formation: The effects of sulfur on metal-silicate partition coefficients

    NASA Astrophysics Data System (ADS)

    Wood, Bernard J.; Kiseeva, Ekaterina S.; Mirolo, Francesca J.

    2014-11-01

    The accretion of the Earth was marked by the high-pressure segregation of the core, accompanied by dissolution of about 10% of one or more “light” elements into the metal. Cosmochemical data suggest that, of these 10% “light” elements, the core contains ∼1.7% S (Dreibus and Palme, 1996) and there is evidence that volatile elements such as S accreted to the Earth late in planetary growth, plausibly as a sulfide “matte” (O'Neill, 1991). Given that metallurgical data indicate that dissolution of even small amounts of sulfur in liquid Fe can have profound effects on the activities of some trace components, we have undertaken a study of the affect of S on the metal-silicate partitioning of a number of the most important chalcophile and siderophile elements. We performed experiments at 1.5 GPa and 1460-1650 °C on metal-silicate partitioning of W, Mo, Ni, Co, Cu, Ag, Mn, Cd, Tl, Cr, Sb, In, Pb, Ga, Ge, V and Zn under conditions where the S content of the metal was varied from 0 to 37 wt%. Mn and Ag were found to exhibit the highest ratio of chalcophile to siderophile behaviour while W, Ga and Sb are the most “chalcophobic” of the elements studied. In terms of the 1-parameter epsilon model (Wagner, 1962) we derived values for each element at 1600 °C as follows (negative values indicate chalcophile behaviour): εCuS = - 2.57; εMnS = - 6.41; εAgS = - 4.15; εSbS = 4.36; εCdS = - 3.78; εInS = - 0.24; εTlS = - 6.21; εGaS = 6.54; εPbS = - 3.73; εCrS = - 3.70; εGeS = 7.03; εVS = - 3.14; εZnS = - 1.68; εMoS = 2.27; εWS = 6.47; εNiS = 2.17; εCoS = 2.40. We use these new data in conjunction with published pressure-temperature dependences of metal-silicate partitioning to test the effects of accreted S on the calculated trace element concentrations in bulk silicate Earth. The approach employs a continuous accretion model in which the oxidation state of the Earth and pressure of core segregation both increase during accretion. We find that, without

  4. 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

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

    PubMed

    Gagné, Olivier Charles; Hawthorne, Frank Christopher

    2016-08-01

    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])Be(2+), ([4])Mg(2+), ([6])Ca(2+), ([6])Sr(2+) and ([6])Ba(2+), 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 Ueq(Na)/Ueq(bonded anions) is partially correlated with 〈([6])Na(+)-O(2-)〉 (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

  6. Metal-Silicate Equilibration at Super-Liquidus Temperatures During Core Formation

    NASA Astrophysics Data System (ADS)

    Hernlund, J. W.; Ichikawa, H.; Labrosse, S.; Kameyama, M.

    2014-12-01

    Experimental constraints on the partitioning of moderately siderophile elements between metal and silicates during core formation suggest equilibration temperatures significantly greater than the liquidus of the silicate Earth (e.g., Wade and Wood, 2005). However, because equilibration was considered to occur in a ponded metal at the silicate solidus, such high temperature equilibration was rejected as implausible. Instead, lower temperature equilibration with variable oxygen fugacity was proposed as an alternative, although the plausibility of the physical mechanisms invoked in this scenario is also questionable. We have re-visited the model of metal-silicate separation in large molten pockets following energetic accretion events, and find that silicate-metal equlibration is most rapid when the iron rains out of the magma, and the release of gravitational potential energy by this rain heats the mixture by as much as 1000 K above the liquidus. However, the first drops of iron rain to pond at the base of the molten pocket will equilibrate at lower temperatures, and only the final drops will be subject to the highest temperatures. We model rain fall and heating of the magma by viscous dissipation to calculate the effective pressure-temperature conditions for partitioning in this scenario, and find that effective pressure conditions are smaller than the pressure at the base of the molten pocket. The ponded metal itself is gravitationally stratified (both in composition and temperature), and is not expected to convect or mix until it undergoes subsequent downward transport into the Earth's core. We also suggest that such a process operating during the very largest giant impact events (extending into the deep mantle) may have given rise to a buoyant oxygen-enriched metal layer atop the outer core, as suggested by some seismological models of the present-day Earth (e.g., Helffrich and Kaneshima, 2010). References: Helffrich, G. and S. Kaneshima (2010), Outer

  7. A study on optical properties of poly (ethylene oxide) based polymer electrolyte with different alkali metal iodides

    NASA Astrophysics Data System (ADS)

    Rao, B. Narasimha; Suvarna, R. Padma

    2016-05-01

    Polymer electrolytes were prepared by adding poly (ethylene glycol) dimethyl ether (PEGDME), TiO2 (nano filler), different alkali metal iodide salts RI (R+=Li+, Na+, K+, Rb+, Cs+) and I2 into Acetonitrile gelated with Poly (ethylene oxide) (PEO). Optical properties of poly (ethylene oxide) based polymer electrolytes were studied by FTIR, UV-Vis spectroscopic techniques. FTIR spectrum reveals that the alkali metal cations were coordinated to ether oxygen of PEO. The optical absorption studies were made in the wavelength range 200-800 nm. It is observed that the optical absorption increases with increase in the radius of alkali metal cation. The optical band gap for allowed direct transitions was evaluated using Urbach-edges method. The optical properties such as optical band gap, refractive index and extinction coefficient were determined. The studied polymer materials are useful for solar cells, super capacitors, fuel cells, gas sensors etc.

  8. Coordination effect-regulated CO2 capture with an alkali metal onium salts/crown ether system

    SciTech Connect

    Yang, Zhen-Zhen; Jiang, Deen; Zhu, Xiang; Tian, Chengcheng; Brown, Suree; Do-Thanh, Chi-Linh; He, Liang-Nian; Dai, Sheng

    2014-01-01

    A coordination effect was employed to realize equimolar CO2 absorption, adopting easily synthesized amino group containing absorbents (alkali metal onium salts). The essence of our strategy was to increase the steric hindrance of cations so as to enhance a carbamic acid pathway for CO2 capture. Our easily synthesized alkali metal amino acid salts or phenolates were coordinated with crown ethers, in which highly sterically hindered cations were obtained through a strong coordination effect of crown ethers with alkali metal cations. For example, a CO2 capacity of 0.99 was attained by potassium prolinate/18-crown-6, being characterized by NMR, FT-IR, and quantum chemistry calculations to go through a carbamic acid formation pathway. The captured CO2 can be stripped under very mild conditions (50 degrees C, N-2). Thus, this protocol offers an alternative for the development of technological innovation towards efficient and low energy processes for carbon capture and sequestration.

  9. Alkali metal carbon dioxide electrochemical system for energy storage and/or conversion of carbon dioxide to oxygen

    NASA Technical Reports Server (NTRS)

    Hagedorn, Norman H. (Inventor)

    1993-01-01

    An alkali metal, such as lithium, is the anodic reactant; carbon dioxide or a mixture of carbon dioxide and carbon monoxide is the cathodic reactant; and carbonate of the alkali metal is the electrolyte in an electrochemical cell for the storage and delivery of electrical energy. Additionally, alkali metal-carbon dioxide battery systems include a plurality of such electrochemical cells. Gold is a preferred catalyst for reducing the carbon dioxide at the cathode. The fuel cell of the invention produces electrochemical energy through the use of an anodic reactant which is extremely energetic and light, and a cathodic reactant which can be extracted from its environment and therefore exacts no transportation penalty. The invention is, therefore, especially useful in extraterrestrial environments.

  10. Effects of spin-exchange collisions in a high-density alkali-metal vapor in low magnetic fields

    SciTech Connect

    Savukov, I.M.; Romalis, M.V.

    2005-02-01

    Spin-exchange collisions often play a dominant role in the broadening of Zeeman resonances in an alkali-metal vapor. Contrary to intuitive expectations, at high alkali-metal densities this broadening can be completely eliminated by operating in a low magnetic field, allowing construction of ultrasensitive atomic magnetometers. We describe a detailed study of the Zeeman resonance frequencies and linewidths as a function of the magnetic field, alkali-metal density, and the degree of spin polarization of the atoms. Due to the nonlinear nature of the density matrix equations describing the spin-exchange collisions both the gyromagnetic ratio and the linewidth change as a function of the polarization. The results of experimental measurements are in excellent agreement with analytical and numerical solutions of the density matrix equations.

  11. [The Measuring Method of Atomic Polarization of Alkali Metal Vapor Based on Optical Rotation and the Analysis of the Influence Factors].

    PubMed

    Shang, Hui-ning; Quan, Wei; Chen, Yao; Li, Yang; Li, Hong

    2016-02-01

    High sensitivity measurements of inertia and magnetic field could be achieved by utilizing a category of devices, which manipulate the atomic spins in the spin-exchange-relaxation-free regime. The alkali cell which contains the alkali metal vapor is used to sense magnetic field and inertia. The atomic number density of alkali vapor and the polarization of alkali metal vapor are two of the most important parameters of the cell. They play an important role in the research on atomic spins in the spin-exchange-relaxation-free regime. Besides, optical polarization plays an important role in quantum computing and atomic physics. We propose a measurement of alkali vapor polarization and alkali number density by detecting the optical rotation in one system. This method simplifies existing experimental equipment and processes. A constant bias magnetic field is applied and the Faraday rotation angle is detected by a bunch of the probe beam to deduce alkali-metal density. Then the magnetic field is closed and a bunch of the pump laser is utilized to polarize alkali-metal. Again, the probe beam is utilized to obtain the polarization of alkali metal. The alkali density obtained at first is used to deduce the polarization. This paper applies a numerical method to analyze the Faraday rotation and the polarization rotation. According to the numerical method, the optimal wavelength for the experiment is given. Finally, the fluctuation of magnetic field and wavelength on signal analysis are analyzed. PMID:27209720

  12. Potential energy curves via double electron-attachment calculations: Dissociation of alkali metal dimers

    NASA Astrophysics Data System (ADS)

    Musiał, Monika; Kowalska-Szojda, Katarzyna; Lyakh, Dmitry I.; Bartlett, Rodney J.

    2013-05-01

    The recently developed method [M. Musiał, J. Chem. Phys. 136, 134111 (2012), 10.1063/1.3700438] to study double electron attached states has been applied to the description of the ground and excited state potential energy curves of the alkali metal dimers. The method is based on the multireference coupled cluster scheme formulated within the Fock space formalism for the (2,0) sector. Due to the use of the efficient intermediate Hamiltonian formulation, the approach is free from the intruder states problem. The description of the neutral alkali metal dimers is accomplished via attaching two electrons to the corresponding doubly ionized system. This way is particularly advantageous when a closed shell molecule dissociates into open shell subunits while its doubly positive cation generates the closed shell fragments. In the current work, we generate the potential energy curves for the ground and multiple excited states of the Li2 and Na2 molecules. In all cases the potential energy curves are smooth for the entire range of interatomic distances (from the equilibrium point to the dissociation limit). Based on the calculated potential energy curves, we are able to compute spectroscopic parameters of the systems studied.

  13. Conducting films of C60 and C70 by alkali-metal doping

    NASA Astrophysics Data System (ADS)

    Haddon, R. C.; Hebard, A. F.; Rosseinsky, M. J.; Murphy, D. W.; Duclos, S. J.

    1991-03-01

    The preparation is reported of alkali-metal-doped films of C60 and C70 which have electrical conductivities at room temperature comparable to those attained by n-type doped polyacetylene. The highest conductivities observed in the doped films are: 4 S/cm (Cs/C60), 100 (Rb/C60), 500 (K/C60), 20 (Na/C60), 10 (Li/C60), 2 (K/C70). The doping process is reversed on exposure of the films to the atmosphere. At high doping level, the films become more resistive. The conductivity induced in these films is attributed to the formation of energy bands from the pi orbitals of C60 or C70, which become partially filled with carriers on doping. The smaller alkali metal ions should be able to fit into the interstices in the lattice without disrupting the network of contacts between the carbon spheroids. In the case of C60, this would allow the development of an isotropic band structure, and it is proposed that these materials may constitute the first three-dimensional 'organic' conductors.

  14. Alkali metal control over N-N cleavage in iron complexes.

    PubMed

    Grubel, Katarzyna; Brennessel, William W; Mercado, Brandon Q; Holland, Patrick L

    2014-12-01

    Though N2 cleavage on K-promoted Fe surfaces is important in the large-scale Haber-Bosch process, there is still ambiguity about the number of Fe atoms involved during the N-N cleaving step and the interactions responsible for the promoting ability of K. This work explores a molecular Fe system for N2 reduction, particularly focusing on the differences in the results obtained using different alkali metals as reductants (Na, K, Rb, Cs). The products of these reactions feature new types of Fe-N2 and Fe-nitride cores. Surprisingly, adding more equivalents of reductant to the system gives a product in which the N-N bond is not cleaved, indicating that the reducing power is not the most important factor that determines the extent of N2 activation. On the other hand, the results suggest that the size of the alkali metal cation can control the number of Fe atoms that can approach N2, which in turn controls the ability to achieve N2 cleavage. The accumulated results indicate that cleaving the triple N-N bond to nitrides is facilitated by simultaneous approach of least three low-valent Fe atoms to a single molecule of N2. PMID:25412468

  15. Alkali and transition metal (Ag, Cu) salts of bridged 5-nitrotetrazole derivatives for energetic applications.

    PubMed

    Klapötke, Thomas M; Sabaté, Carles Miró; Rasp, Matthias

    2009-03-14

    A family of energetic salts based on the novel 5-(5-nitrotetrazole-2-ylmethyl)-tetrazolate anion (NTTz(-)) with alkali metals (Li(+), Na(+), K(+), Rb(+) and Cs(+)) were synthesized by the reaction of the free acid 5-(5-nitrotetrazole-2-ylmethyl)-tetrazole with a suitable alkali metal base (bicarbonate or carbonate) in alcohol or water. The sodium salt () was, in turn, used to form salts containing the NTTz(-) anion and Ag(+) () or Cu(2+) (, and ) cations. The new compounds were characterized by IR, Raman and NMR spectroscopy, mass spectroscopy, elemental analysis and differential scanning calorimetry (DSC). In addition, the solid-state structure of the NTTz(-) anion was determined by diffraction methods using X-ray analysis. We also assessed the energetic properties of the compounds using standardized (BAM) tests. Interestingly, the silver and copper salts are easily and safely initiated by the laser beam generated by a Raman machine and some of the compounds reported here have promising properties for applications as a new class of nitrogen-rich, more environmentally-friendly energetic materials. PMID:19240918

  16. Adiabatic hyperspherical study of weakly bound helium-helium-alkali-metal triatomic systems

    SciTech Connect

    Suno, Hiroya; Esry, B. D.

    2010-12-15

    {sup 4}He{sub 2}-alkali-metal triatomic molecular systems are studied using the adiabatic hyperspherical representation. By adopting the best pairwise He-He and He-X interaction potentials, we search for weakly bound states of {sup 4}He{sub 2}X systems with X={sup 6}Li, {sup 7}Li, {sup 23}Na, {sup 39}K, {sup 40}K, {sup 41}K, {sup 85}Rb, {sup 87}Rb, and {sup 133}Cs. We consider not only zero total angular momentum J=0 states, but also J>0 states. We find that the {sup 4}He{sub 2}{sup 6}Li and {sup 4}He{sub 2}{sup 7}Li systems each possess two bound states with J{sup {Pi}=}0{sup +} symmetry and none with J>0, while the other {sup 4}He{sub 2}-alkali-metal species are found to support one 0{sup +} and one 1{sup -} bound state. We calculate the bound-state energies of these molecular species and discuss the essential features of the wave functions associated with these bound states.

  17. Higher-order C{sub n} dispersion coefficients for the alkali-metal atoms

    SciTech Connect

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

    2005-04-01

    The van der Waals coefficients, from C{sub 11} through to C{sub 16} resulting from second-, third-, and fourth-order perturbation theory are estimated for the alkali-metal (Li, Na, K, and Rb) atoms. The dispersion coefficients are also computed for all possible combinations of the alkali-metal atoms and hydrogen. The parameters are determined from sum rules after diagonalizing a semiempirical fixed core Hamiltonian in a large basis. Comparisons of the radial dependence of the C{sub n}/r{sup n} potentials give guidance as to the radial regions in which the various higher-order terms can be neglected. It is seen that including terms up to C{sub 10}/r{sup 10} results in a dispersion interaction that is accurate to better than 1% whenever the inter-nuclear spacing is larger than 20a{sub 0}. This level of accuracy is mainly achieved due to the fortuitous cancellation between the repulsive (C{sub 11},C{sub 13},C{sub 15}) and attractive (C{sub 12},C{sub 14},C{sub 16}) dispersion forces.

  18. 3718-F Alkali Metal Treatment and Storage Facility Closure Plan. Revision 1

    SciTech Connect

    1992-11-01

    The Hanford Site, located northwest of the city of Richland, Washington, houses reactors, chemical-separation systems, and related facilities used for the production of special nuclear materials, as well as for activities associated with nuclear energy development. The 300 Area of the Hanford Site contains reactor fuel manufacturing facilities and several research and development laboratories. The 3718-F Alkali Metal Treatment and Storage Facility (3718-F Facility), located in the 300 Area, was used to store and treat alkali metal wastes. Therefore, it is subject to the regulatory requirements for the storage and treatment of dangerous wastes. Closure will be conducted pursuant to the requirements of the Washington Administrative Code (WAC) 173-303-610 (Ecology 1989) and 40 CFR 270.1. Closure also will satisfy the thermal treatment facility closure requirements of 40 CFR 265.381. This closure plan presents a description of the 3718-F Facility, the history of wastes managed, and the approach that will be followed to close the facility. Only hazardous constituents derived from 3718-F Facility operations will be addressed.

  19. 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.

  20. Alkali Metal Control over N–N Cleavage in Iron Complexes

    PubMed Central

    2015-01-01

    Though N2 cleavage on K-promoted Fe surfaces is important in the large-scale Haber–Bosch process, there is still ambiguity about the number of Fe atoms involved during the N–N cleaving step and the interactions responsible for the promoting ability of K. This work explores a molecular Fe system for N2 reduction, particularly focusing on the differences in the results obtained using different alkali metals as reductants (Na, K, Rb, Cs). The products of these reactions feature new types of Fe–N2 and Fe-nitride cores. Surprisingly, adding more equivalents of reductant to the system gives a product in which the N–N bond is not cleaved, indicating that the reducing power is not the most important factor that determines the extent of N2 activation. On the other hand, the results suggest that the size of the alkali metal cation can control the number of Fe atoms that can approach N2, which in turn controls the ability to achieve N2 cleavage. The accumulated results indicate that cleaving the triple N–N bond to nitrides is facilitated by simultaneous approach of least three low-valent Fe atoms to a single molecule of N2. PMID:25412468

  1. Lanthanoid/Alkali Metal β-Triketonate Assemblies: A Robust Platform for Efficient NIR Emitters.

    PubMed

    Reid, Brodie L; Stagni, Stefano; Malicka, Joanna M; Cocchi, Massimo; Sobolev, Alexandre N; Skelton, Brian W; Moore, Evan G; Hanan, Garry S; Ogden, Mark I; Massi, Massimiliano

    2015-12-01

    The reaction of hydrated lanthanoid chlorides with tribenzoylmethane and an alkali metal hydroxide consistently resulted in the crystallization of neutral tetranuclear assemblies with the general formula [Ln(Ae⋅HOEt)(L)4 ]2 (Ln=Eu(3+) , Er(3+) , Yb(3+) ; Ae=Na(+) , K(+) , Rb(+) ). Analysis of the crystal structures of these species revealed a coordination geometry that varied from a slightly distorted square antiprism to a slightly distorted triangular dodecahedron, with the specific geometrical shape being dependent on the degree of lattice solvation and identity of the alkali metal. The near-infrared (NIR)-emitting assemblies of Yb(3+) and Er(3+) showed remarkably efficient emission, characterized by significantly longer excited-state lifetimes (τobs ≈37-47 μs for Yb(3+) and τobs ≈4-6 μs for Er(3+) ) when compared with the broader family of lanthanoid β-diketonate species, even in the case of perfluorination of the ligands. The Eu(3+) assemblies show bright red emission and a luminescence performance (τobs ≈0.5 ms, ${{\\Phi}{{{\\rm L}\\hfill \\atop {\\rm Ln}\\hfill}}}$≈35-37 %, ηsens ≈68-70 %) more akin to the β-diketonate species. The results highlight that the β-triketonate ligand offers a tunable and facile system for the preparation of efficient NIR emitters without the need for more complicated perfluorination or deuteration synthetic strategies. PMID:26511032

  2. Formation of Metal and Silicate Globules in Gujba: A New Bencubbin-like Meteorite Fall

    NASA Technical Reports Server (NTRS)

    Rubin, Alan E.; Kallemeyn, Gregory W.; Wasson, John T.; Clayton, Robert N.; Mayeda, Toshiko; Grady, Monica; Verchovsky, Alexander B.; Eugster, Otto; Lorenzetti, Silvio

    2006-01-01

    Gujba is a coarse-grained meteorite fall composed of 41 vol% large kamacite globules, 20 vol% large light-colored silicate globules with cryptocrystalline, barred pyroxene and barred olivine textures, 39 vol% dark-colored, silicate-rich matrix, and rare refractory inclusions. Gujba resembles Bencubbin and Weatherford in texture, oxygen-isotopic composition and in having high bulk delta N-15 values (approximately +685%0). The He-3 cosmic-ray exposure age of Gujba (26 +/- 7 Ma) is essentially identical to that of Bencubbin, suggesting that they were both reduced to meter-size fragments in the same parent-body collision. The Gujba metal globules exhibit metal-troilite quench textures and vary in their abundances of troilite and volatile siderophile elements. We suggest that the metal globules formed as liquid droplets either via condensation in an impact-generated vapor plume or by evaporation of preexisting metal particles in a plume. The lower the abundance of volatile elements in the metal globules, the higher the globule quench temperature. We infer that the large silicate globules also formed from completely molten droplets; their low volatile-element abundances indicate that they also formed at high temperatures, probably by processes analogous to those that formed the metal globules. The coarse-grained Bencubbin-Weatherford-Gujba meteorites may represent a depositional component from the vapor cloud enriched in coarse and dense particles. A second class of Bencubbin-like meteorites (represented by Hammadah a1 Hamra 237 and QUE 94411) may be a finer fraction derived from the same vapor cloud

  3. Silicate Inclusions in the Kodaikanal IIE Iron Meteorite

    NASA Technical Reports Server (NTRS)

    Kurat, G.; Varela, M. E.; Zinner, E.

    2005-01-01

    Silicate inclusions in iron meteorites display an astonishing chemical and mineralogical variety, ranging from chondritic to highly fractionated, silica- and alkali-rich assemblages. In spite of this, their origin is commonly considered to be a simple one: mixing of silicates, fractionated or unfractionated, with metal. The latter had to be liquid in order to accommodate the former in a pore-free way which all models accomplish by assuming shock melting. II-E iron meteorites are particularly interesting because they contain an exotic zoo of silicate inclusions, including some chemically strongly fractionated ones. They also pose a formidable conundrum: young silicates are enclosed by very old metal. This and many other incompatibilities between models and reality forced the formulation of an alternative genetic model for irons. Here we present preliminary findings in our study of Kodaikanal silicate inclusions.

  4. First-principles study of d0 ferromagnetism in alkali-metal doped GaN

    NASA Astrophysics Data System (ADS)

    Zhang, Yong

    2016-08-01

    The d0 ferromagnetism in GaN has been studied based on density functional theory. Our results show that GaN with sufficient hole become spin-polarized. Alkali-metal doping can introduce holes in GaN. Among them, both of Li- and Na-doping induce ferromagnetism in GaN and Na-doped GaN behaves as half-metallic ferromagnet. Moreover, at a growth temperature of 2000 K under N-rich condition, both concentrations can exceed 18%, which is sufficient to produce detectable macroscopic magnetism in GaN. The Curie temperature of Li- and Na-doped GaN is estimated to be 304 and 740 K, respectively, which are well above room temperature.

  5. Ab initio interaction potentials and scattering lengths for ultracold mixtures of metastable helium and alkali-metal atoms

    NASA Astrophysics Data System (ADS)

    Kedziera, Dariusz; Mentel, Łukasz; Żuchowski, Piotr S.; Knoop, Steven

    2015-06-01

    We have obtained accurate ab initio +4Σ quartet potentials for the diatomic metastable triplet helium+alkali-metal (Li, Na, K, Rb) systems, using all-electron restricted open-shell coupled cluster singles and doubles with noniterative triples corrections CCSD(T) calculations and accurate calculations of the long-range C6 coefficients. These potentials provide accurate ab initio quartet scattering lengths, which for these many-electron systems is possible, because of the small reduced masses and shallow potentials that result in a small amount of bound states. Our results are relevant for ultracold metastable triplet helium+alkali-metal mixture experiments.

  6. Theoretical analysis of oxygen diffusion at startup in an alkali metal heat pipe with gettered alloy walls

    NASA Technical Reports Server (NTRS)

    Tower, L. K.

    1973-01-01

    The diffusion of oxygen into, or out of, a gettered alloy exposed to oxygenated alkali liquid metal coolant, a situation arising in some high temperature heat transfer systems, was analyzed. The relation between the diffusion process and the thermochemistry of oxygen in the alloy and in the alkali metal was developed by making several simplifying assumptions. The treatment is therefore theoretical in nature. However, a practical example pertaining to the startup of a heat pipe with walls of T-111, a tantalum alloy, and lithium working fluid illustrates the use of the figures contained in the analysis.

  7. 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.

  8. Siderophile elements and metal-silicate fractionation in the solar nebula

    NASA Technical Reports Server (NTRS)

    Newsom, H. E.

    1994-01-01

    The most important nebular fractionation affecting the siderophile elements is the metal-silicate fractionation process and its relationship to the chondrule formation process is poorly understood. Understanding these processes is important in terms of understanding the expected compositional range for planetary building blocks. In a general way the composition of chondrites can be derived from the composition of the CI chondrites by addition or subtraction of a refractory component similar to CAI's (in some cases with a Mg2SiO4 component) and by addition or subtraction of Fe metal. Thus normalization to Fe produces the least spread in the normalized abundances of most siderophile elements relative to CI abundances. Detailed bulk chemical studies of chondrules have shown that their siderophile elements have refractory-element siderophile-element signatures (for example, Ir/Ni) that are similar to the bulk meteorites, but distinct among the different chondrite groups. This data suggests that the chondrules were not supplied to the chondrule groups from a single homogeneous source, and that each chondrite group's characteristic siderophile-element signature was established before chondrule formation. These authors make a further inference that all siderophile-lithophile-element fractionation occurred before chondrule formation, but recent discoveries and observations suggest this is not true. The discovery of the metal-rich CH meteorites, the recognition of the role of aerodynamic forces in the solar nebula, and the possible role of metal-silicate segregation during the chondrule formation process suggests that metal-silicate fractionation occurred before, during and after chondrule formation.

  9. Cementitious binders from activated stainless steel refining slag and the effect of alkali solutions.

    PubMed

    Salman, Muhammad; Cizer, Özlem; Pontikes, Yiannis; Snellings, Ruben; Vandewalle, Lucie; Blanpain, Bart; Van Balen, Koen

    2015-04-01

    With an aim of producing high value cementitious binder, stainless steel refining slag containing a high amount of CaO in γ-dicalcium silicate form was activated with NaOH and Na-silicate as well as KOH and K-silicate solutions, followed by steam curing at 80 °C. Higher levels of alkali-silicate in the activating solution resulted in higher cumulative heat suggesting accelerated reaction kinetics. With respect to compressive strength, higher levels of alkali silicate resulted in higher strength and the mortars with Na activator were found to have higher early strength than the ones with K activator. The long term strength was found to be similar, regardless of the alkali metal. Thermogravimetric, QXRD and FTIR analyses showed an increase in the amount of reaction products (C-S-H type) over time, further confirming the reactivity of the crystalline slag. Batch leaching results showed lower leaching of heavy metals and metalloids with K activator compared to the Na activator. These results demonstrate that the alkali type and the ratio of hydroxide to silicates have a significant impact on the hydration and mechanical strength development of the stainless steel slag. The above findings can aid in the recycling and valorization of these type of slags which otherwise end up landfilled. PMID:25577317

  10. Platinum partitioning between metal and silicate melts: Core formation, late veneer and the nanonuggets issue

    NASA Astrophysics Data System (ADS)

    Médard, Etienne; Schmidt, Max W.; Wälle, Markus; Keller, Nicole S.; Günther, Detlef

    2015-08-01

    High-pressure, high-temperature experiments have been performed at ∼1.2 GPa and 1360-2100 °C to investigate the partitioning of Pt between a silicate melt and a metallic melt. Our experiments indicate that nanonuggets encountered in previous experiments are experimental artifacts, formed at high temperature by oversaturation caused by high oxygen fugacity during the initial stages of an experiment. Experiments at high-acceleration using a centrifuging piston-cylinder show that nanonuggets can be removed by gravity during the experiment. Formation of nanonuggets can also be avoided by using initially reduced starting materials. The presence of iron is also a key element in reducing the formation of nanonuggets. Our nanonugget-free data are broadly consistent with previous nanonuggets-filtered data, and suggest that Pt partitioning becomes independent of oxygen fugacity below an oxygen fugacity of at least IW+2. Pt is thus possibly dissolved as a neutral species (or even an anionic species) at low fO2, instead of the more common Pt2+ species present at higher fO2. Due to low concentration, the nature of this species cannot be determined, but atomic Pt or Pt- are possible options. Under core-formation conditions, Pt partitioning between metal and silicate is mostly independent of oxygen fugacity, silicate melt composition, and pressure. Partition coefficient during core formation can be expressed by the following equation: log DPtMmetal/silicate = 1.0348 + 14698 / T (in weight units). Calculations indicate that the Pt content (and by extension the Highly Siderophile Elements content) of the Earth's mantle cannot be explained by equilibrium partitioning during core formation, requiring further addition of HSE to the mantle. The mass of this late veneer is approximately 0.4% of the total mass of the Earth (or 0.6% of the mass of the mantle).

  11. Extent of metal-silicate disequilibrium during accretion and early differentiation of the Earth

    NASA Astrophysics Data System (ADS)

    Rubie, D. C.; Nimmo, F.; Morbidelli, A.; Frost, D. J.

    2012-12-01

    Earth, Mars, Venus and Mercury accreted on a timescale of 10-100 My through a series of violent collisions with planetesimals and embryos. The high energy of such impacts was sufficient to cause deep magma ocean formation which facilitated the segregation of metal and silicate liquids. Planetary cores thus formed as a multistage process that was inseparable from the accretion process. In order to better understand the formation and early differentiation of the terrestrial planets, we are integrating a multistage core-formation model with N-body accretion simulations. Constraints on model parameters are the compositions of the Earth's primitive mantle and, to a lesser extent, the mantles of Mars and Mercury which may be FeO rich and FeO-poor respectively. We use a least-squares minimization to optimise 4 model parameters. Elements currently considered include Si, O, Ni, Co, W, Nb, Cr, Ta and V. We concentrate on recent N-body simulations that result in an approximately Earth-mass planet at ~1 AU. In order to satisfy the model constraints, accretion has to be heterogeneous, with embryos and planetesimals originating in the inner part of the solar system (e.g. <1.5 AU) being highly reduced and those from further out being more oxidised. Metal-silicate equilibration pressures are high (e.g. ~0.75 x evolving CMB pressures). The model enables estimations of (1) the extent to which the metallic cores of impactors emulsify and equilibrate in a magma ocean and (2) the fraction of magma oceans that are involved in the equilibration process for both impacting planetesimals and embryos. Both estimates are crucial for interpreting Hf-W age determinations. Best results are obtained when the fraction of silicate mantle/magma ocean that interacts chemically with the metallic cores of impactors is limited and lies in the range 0.003 to 0.1, depending on the size of the impactor and magma ocean depth. The degree of incomplete metal equilibration depends on the extent to which the

  12. Influence of calcium chloride on the thermal behavior of heavy and alkali metals in sewage sludge incineration.

    PubMed

    Han, Jun; Xu, Minghou; Yao, Hong; Furuuchi, Masami; Sakano, Takeo; Kim, Hee Joon

    2008-01-01

    In order to separate and reuse heavy and alkali metals from flue gas during sewage sludge incineration, experiments were carried out in a pilot incinerator. The experimental results show that most of the heavy and alkali metals form condensed phase at temperature above 600 degrees C. With the addition of 5% calcium chloride into sewage sludge, the gas/solid transformation temperature of part of the metals (As, Cu, Mg and Na) is evidently decreased due to the formation of chloride, while calcium chloride seems to have no significant influence on Zn and P. Moreover, the mass fractions of some heavy and alkali metals in the collected fly ash are relatively high. For example, the mass fractions for Pb and Cu in the fly ash collected by the filter are 1.19% and 19.7%, respectively, which are well above those in lead and copper ores. In the case of adding 5% calcium chloride, the heavy and alkali metals can be divided into three groups based on their conversion temperature: Group A that includes Na, Zn, K, Mg and P, which are converted into condensed phase above 600 degrees C; Group B that includes Pb and Cu which solidify when the temperature is above 400 degrees C; and Group C that includes As, whose condensation temperature is as low as 300 degrees C. PMID:17412581

  13. James C. McGroddy Prize Talk: Superconductivity in alkali-metal doped Carbon-60

    NASA Astrophysics Data System (ADS)

    Hebard, Arthur

    2008-03-01

    Carbon sixty (C60), which was first identified in 1985 in laser desorption experiments, is unquestionably an arrestingly beautiful molecule. The high symmetry of the 12 pentagonal and 20 hexagonal faces symmetrically arrayed in a soccer-ball like structure invites special attention and continues to stimulate animated speculation. The availability in 1990 of macroscopic amounts of purified C60 derived from carbon-arc produced soot allowed the growth and characterization of both bulk and thin-film samples. Crystalline C60 is a molecular solid held together by weak van der Waals forces. The fcc structure has a 74% packing fraction thus allowing ample opportunity (26% available volume) for the intercalation of foreign atoms into the interstitial spaces of the three dimensional host. This opportunity catalyzed much of the collaborative work amongst chemists, physicists and materials scientists at Bell Laboratories, and resulted in the discovery of superconductivity in alkali-metal doped C60 with transition temperatures (Tc) in the mid-30-kelvin range. In this talk I will review how the successes of this initial team effort stimulated a worldwide collaboration between experimentalists and theorists to understand the promise and potential of an entirely new class of superconductors containing only two elements, carbon and an intercalated alkali metal. Although the cuprates still hold the record for the highest Tc, there are still open scientific questions about the mechanism that gives rise to such unexpectedly high Tc's in the non-oxide carbon-based superconductors. The doped fullerenes have unusual attributes (e.g., narrow electronic bands, high disorder, anomalous energy scales, and a tantalizing proximity to a metal-insulator Mott transition), which challenge conventional thinking and at the same time provide useful insights into new directions for finding even higher Tc materials. The final chapter of the `soot to superconductivity' story has yet to be written.

  14. Characterization of carbonated tricalcium silicate and its sorption capacity for heavy metals: a micron-scale composite adsorbent of active silicate gel and calcite.

    PubMed

    Chen, Quanyuan; Hills, Colin D; Yuan, Menghong; Liu, Huanhuan; Tyrer, Mark

    2008-05-01

    Adsorption-based processes are widely used in the treatment of dilute metal-bearing wastewaters. The development of versatile, low-cost adsorbents is the subject of continuing interest. This paper examines the preparation, characterization and performance of a micro-scale composite adsorbent composed of silica gel (15.9 w/w%), calcium silicate hydrate gel (8.2 w/w%) and calcite (75.9 w/w%), produced by the accelerated carbonation of tricalcium silicate (C(3)S, Ca(3)SiO(5)). The Ca/Si ratio of calcium silicate hydrate gel (C-S-H) was determined at 0.12 (DTA/TG), 0.17 ((29)Si solid-state MAS/NMR) and 0.18 (SEM/EDS). The metals-retention capacity for selected Cu(II), Pb(II), Zn(II) and Cr(III) was determined by batch and column sorption experiments utilizing nitrate solutions. The effects of metal ion concentration, pH and contact time on binding ability was investigated by kinetic and equilibrium adsorption isotherm studies. The adsorption capacity for Pb(II), Cr(III), Zn(II) and Cu(II) was found to be 94.4 mg/g, 83.0 mg/g, 52.1 mg/g and 31.4 mg/g, respectively. It is concluded that the composite adsorbent has considerable potential for the treatment of industrial wastewater containing heavy metals. PMID:17950999

  15. Alkali metal vapor removal from pressurized fluidized-bed combustor flue gas. Quarterly report, April-June 1980

    SciTech Connect

    Johnson, I.; Swift, W.M.; Lee, S.H.D.; Boyd, W.A.

    1980-07-01

    In the application of pressurized fluidized-bed combustors (PFBC) to the generation of electricity, hot corrosion of gas turbine components by alkali metal compounds is a potential problem. The objective of this investigation is to develop a method for removing these gaseous alkali metal compounds from the high-pressure high-temperature gas from a PFBC before the gas enters the gas turbine. A granular-bed filter, using either diatomaceous earth or activated bauxite as the bed material, is the concept currently being studied. Results are presented for the testing of diatomaceous earth for alkali vapor sorption at 800/sup 0/C and 9-atm pressure, using a simulated flue gas. Activated bauxite sorbent can be regenerated by leaching with water, and the kinetics of the leaching is under study.

  16. Investigation of anti-Relaxation coatings for alkali-metal vapor cells using surface science techniques

    SciTech Connect

    Seltzer, S. J.; Michalak, D. J.; Donaldson, M. H.; Balabas, M. V.; Barber, S. K.; Bernasek, S. L.; Bouchiat, M.-A.; Hexemer, A.; Hibberd, A. M.; Jackson Kimball, D. F.; Jaye, C.; Karaulanov, T.; Narducci, F. A.; Rangwala, S. A.; Robinson, H. G.; Shmakov, A. K.; Voronov, D. L.; Yashchuk, V. V.; Pines, A.; Budker, D.

    2010-10-11

    Many technologies based on cells containing alkali-metal atomic vapor benefit from the use of antirelaxation surface coatings in order to preserve atomic spin polarization. In particular, paraffin has been used for this purpose for several decades and has been demonstrated to allow an atom to experience up to 10?000 collisions with the walls of its container without depolarizing, but the details of its operation remain poorly understood. We apply modern surface and bulk techniques to the study of paraffin coatings in order to characterize the properties that enable the effective preservation of alkali spin polarization. These methods include Fourier transform infrared spectroscopy, differential scanning calorimetry, atomic force microscopy, near-edge x-ray absorption fine structure spectroscopy, and x-ray photoelectron spectroscopy. We also compare the light-induced atomic desorption yields of several different paraffin materials. Experimental results include the determination that crystallinity of the coating material is unnecessary, and the detection of C=C double bonds present within a particular class of effective paraffin coatings. Further study should lead to the development of more robust paraffin antirelaxation coatings, as well as the design and synthesis of new classes of coating materials.

  17. Silicon halide-alkali metal flames as a source of solar grade silicon

    NASA Technical Reports Server (NTRS)

    Olsen, D. B.; Miller, W. J.

    1979-01-01

    The feasibility of using alkali metal-silicon halide diffusion flames to produce solar-grade silicon in large quantities and at low cost is demonstrated. Prior work shows that these flames are stable and that relatively high purity silicon can be produced using Na + SiCl4 flames. Silicon of similar purity is obtained from Na + SiF4 flames although yields are lower and product separation and collection are less thermochemically favored. Continuous separation of silicon from the byproduct alkali salt was demonstrated in a heated graphite reactor. The process was scaled up to reduce heat losses and to produce larger samples of silicon. Reagent delivery systems, scaled by a factor of 25, were built and operated at a production rate of 0.5 kg Si/h. Very rapid reactor heating rates are observed with wall temperatures reaching greater than 2000 K. Heat release parameters were measured using a cooled stainless steel reactor tube. A new reactor was designed.

  18. 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)].

  19. Highly sensitive sensors for alkali metal ions based on complementary-metal-oxide-semiconductor-compatible silicon nanowires

    NASA Astrophysics Data System (ADS)

    Zhang, Guo-Jun; Agarwal, Ajay; Buddharaju, Kavitha D.; Singh, Navab; Gao, Zhiqiang

    2007-06-01

    Highly sensitive sensors for alkali metal ions based on complementary-metal-oxide- semiconductor-compatible silicon nanowires (SiNWs) with crown ethers covalently immobilized on their surface are presented. A densely packed organic monolayer terminated with amine groups is introduced to the SiNW surface via hydrosilylation. Amine-modified crown ethers, acting as sensing elements, are then immobilized onto the SiNWs through a cross-linking reaction with the monolayer. The crown ether-functionalized SiNWs recognize Na+ and K+ according to their complexation ability to the crown ethers. The SiNW sensors are highly selective and capable of achieving an ultralow detection limit down to 50nM, over three orders of magnitude lower than that of conventional crown ether-based ion-selective electrodes.

  20. The Origin of Chondrites: Metal-Silicate Separation Experiments Under Microgravity Conditions, Experiment 2

    NASA Technical Reports Server (NTRS)

    Moore, S. R.; Franzen, M.; Benoit, P. H.; Sears, D. W. G.; Holley, A.; Myers, M.; Godsey, R.; Czlapinski, J.

    2003-01-01

    Chondrites are categorized into different groups by several properties, including the metal-to-silicate ratio. Various processes have been suggested to produce distinct metal/silicate ratios, some based on sorting in the early solar nebular and others occurring after accretion on the parent body. Huang et al. suggested that a weak gravitational field accompanied by degassing, could result in metal/silicate separation on parent bodies. We suggest that asteroids were volatile-rich, at least early in their histories. Spectroscopic evidence from asteroid surfaces indicates that one-third of all asteroids maybe rich in clays and hydrated minerals, similar to carbonaceous chondrites. Internal and/or external heating could have caused volatiles to evaporate and pass through a surface dust layer. Spacecraft images of asteroids show they have a thick regoliths. Housen, and Asphaug and Nolan proposed that even a 10 km diameter asteroid could potentially have a significant regolith. Grain size and grain density sorting could occur in the unconsolidated layer by the process known as fluidization. This process occurs when an upward stream of gas is passed through a bed of particles which are lifted against a gravitational force. Fluidization is commonly used commercially to sort particulates. This type of behavior is based upon the bed, as a whole, and differs from aerodynamic sorting. Two sets of reduced gravity experiments were conducted during parabolic flights aboard NASA's KC-135 aircraft. The first experiment employed 310 tubes of 2.5 cm diameter, containing mixtures of sand and metal grains. A gas source was used to fluidize the mixture at reduced gravity conditions and mixtures were analyzed after the flight. However, this experiment did not allow a description of the fluidization as a function of gravity. A second experiment was conducted on the KC-135 aircraft in the summer of 2001, consisting of two Plexiglas cylinders containing a metal/silicate mixture, and video

  1. Electrical Transport Properties of C60 Single Crystals Doped with Alkali Metals

    NASA Astrophysics Data System (ADS)

    Ogata, Hironori; Maruyama, Yusei; Inabe, Tamotsu; Achiba, Yohji; Suzuki, Sinzo; Kikuchi, Koichi; Ikemoto, Isao

    Electronic structures of various kinds of alkali metal (Na, K, Rb or Cs)-doped C60 solids are studied by electrical resistivity and thermoelectric power measurements by using C60 single crystals prepared from a CS2 solution as a starting material. For K-or Rb-doped C60, metallic conducting behaviors in the normal conducting state and relatively sharp superconducting transitions are observed by the electrical resistivity measurements. Nearly linear-temperature dependences with the negative sign are observed in the thermoelectric power measurements at the normal conducting states for K-or Rb-doped C60. From electron diffusion term of the thermoelectric power, the values of Fermi energy and the density of states at the Fermi energy are estimated by assuming the three-dimensional free electron model, which are in substantial agreement with the results of other experiments and calculations. "Metal-semiconductor transition" is observed in both the electrical resistivity and the thermoelectric power measurements for Na-doped C60. Existence of metallic phase is confirmed by the thermoelectric power measurement in Cs-doped C60.

  2. Mechanism for alkali metal-catalyzed CO/sub 2/ gasification of carbon

    SciTech Connect

    Saber, J.M.

    1987-01-01

    Alkali metal-catalyzed gasification of carbon by CO/sub 2/ was studied using Temperature-programmed reaction and isotopic tracers. Between 500 and 1000 K, oxide groups on the carbon surface interact with potassium carbonate to form carbonate/oxygen/carbon complexes. The complexes exchange carbon and oxygen isotopes readily with gas-phase carbon dioxide. Sodium carbonate, however, does not appear to complex with the surface oxide groups under these conditions. The surface oxide groups also stabilize potassium on the carbon surface, thus, less potassium volatilizes from higher-oxygen-content carbons than from lower oxygen content carbons. Above 1000 K, both potassium and sodium carbonate decompose coincident with catalyzed CO/sub 2/ gasification to form a metal oxide with a metal:oxygen ratio of 2. The oxide can be oxidized to give a metal:0 ratio of 1. The carbonate does not appear to be the catalytically active species. Reactions describing Na-catalyzed gasification via oxygen. Transfer mechanisms are proposed.

  3. Adsorption properties of carbon materials produced by thermolysis of brown coal in the presence of alkali metal hydroxides

    SciTech Connect

    Tamarkina, Y.V.; Maslova, L.A.; Khabarova, T.V.; Kucherenko, V.A.

    2008-07-15

    Activated carbons produced by thermolysis of brown coal impregnated with an alkali metal hydroxide MOH (M = Li, Na, K) at an MOH/coal ratio R-MOH = 80 mol kg{sup -1} were studied. Dependences of the adsorption capacities for iodine and Methylene Blue dye, specific surface area, and yield of activated carbons on the ratio R-MOH were obtained.

  4. The role of alkali metal cations in the stabilization of guanine quadruplexes: why K(+) is the best.

    PubMed

    Zaccaria, F; Paragi, G; Fonseca Guerra, C

    2016-08-21

    The alkali metal ion affinity of guanine quadruplexes has been studied using dispersion-corrected density functional theory (DFT-D). We have done computational investigations in aqueous solution that mimics artificial supramolecular conditions where guanine bases assemble into stacked quartets as well as biological environments in which telomeric quadruplexes are formed. In both cases, an alkali metal cation is needed to assist self-assembly. Our quantum chemical computations on these supramolecular systems are able to reproduce the experimental order of affinity of the guanine quadruplexes for the cations Li(+), Na(+), K(+), Rb(+), and Cs(+). The strongest binding is computed between the potassium cation and the quadruplex as it occurs in nature. The desolvation and the size of alkali metal cations are thought to be responsible for the order of affinity. Until now, the relative importance of these two factors has remained unclear and debated. By assessing the quantum chemical 'size' of the cation, determining the amount of deformation of the quadruplex needed to accommodate the cation and through the energy decomposition analysis (EDA) of the interaction energy between the cation and the guanines, we reveal that the desolvation and size of the alkali metal cation are both almost equally responsible for the order of affinity. PMID:27185388

  5. Electric dipole polarizabilities at imaginary frequencies for hydrogen, the alkali-metal, alkaline-earth, and noble gas atoms

    SciTech Connect

    Derevianko, Andrei Porsev, Sergey G. Babb, James F.

    2010-05-15

    The electric dipole polarizabilities evaluated at imaginary frequencies for hydrogen, the alkali-metal atoms, the alkaline-earth atoms, and the noble gases are tabulated along with the resulting values of the atomic static polarizabilities, the atom-surface interaction constants, and the dispersion (or van der Waals) constants for the homonuclear and the heteronuclear diatomic combinations of the atoms.

  6. Spin-axis relaxation in spin-exchange collisions of alkali-metal atoms

    NASA Astrophysics Data System (ADS)

    Kadlecek, S.; Walker, T.; Walter, D. K.; Erickson, C.; Happer, W.

    2001-05-01

    We present calculations of spin-relaxation rates of alkali-metal atoms due to the spin-axis interaction acting in binary collisions between the atoms. We show that for the high-temperature conditions of interest here, the spin-relaxation rates calculated with classical-path trajectories are nearly the same as those calculated with the distorted-wave Born approximation. We compare these calculations to recent experiments that used magnetic decoupling to isolate spin relaxation due to binary collisions from that due to the formation of triplet van der Waals molecules. The values of the spin-axis coupling coefficients deduced from measurements of binary collision rates are consistent with those deduced from molecular decoupling experiments, and follow a physically plausible scaling law for the spin-axis coupling coefficients.

  7. Spin-exchange frequency shift in alkali-metal-vapor cell frequency standards

    SciTech Connect

    Micalizio, Salvatore; Godone, Aldo; Levi, Filippo; Vanier, Jacques

    2006-03-15

    In this paper we calculate the effect of spin-exchange collisions in alkali-metal vapors. In the framework of the high-energy approximation, we evaluate the spin-exchange cross sections related to the line broadening and to the frequency shift of the ground state hyperfine transition. We do the calculation for the four isotopes, {sup 23}Na, {sup 39}K, {sup 87}Rb, and {sup 133}Cs. The results are used in particular to evaluate the spin-exchange frequency shift in Rb vapor cell frequency standards used in many applications. It turns out that, due to possible fluctuations in the atomic density, spin exchange may affect significantly the medium and long term frequency stability of the frequency standard.

  8. Silicon Halide-alkali Metal Flames as a Source of Solar Grade Silicon

    NASA Technical Reports Server (NTRS)

    Olson, D. B.; Gould, R. K.

    1979-01-01

    A program is presented which was aimed at determining the feasibility of using high temperature reactions of alkali metals and silicon halides to produce low cost solar-grade silicon. Experiments are being conducted to evaluate product separation and collection processes, measure heat release parameters for scaling purposes, and determine the effects of the reactants and/or products on materials of reactor construction. During the current reporting period, the results of heat release experiments were used to design and construct a new type of thick-wall graphite reactor to produce larger quantities of silicon. A reactor test facility was constructed. Material compatibility tests were performed for Na in contact with graphite and several coated graphites. All samples were rapidly degraded at T = 1200K, while samples retained structural strength at 1700K. Pyrolytic graphite coatings cracked and separated from substances in all cases.

  9. Measurements of positron scattering by hydrogen, alkali metal, and other atoms

    NASA Astrophysics Data System (ADS)

    Stein, T. S.; Harte, M.; Jiang, J.; Kauppila, W. E.; Kwan, C. K.; Li, H.; Zhou, S.

    1998-08-01

    Recent developments in measurements of total and positronium (Ps) formation cross sections for positrons (in the energy range of 1-300 eV) scattered by hydrogen, alkali metal, and other atoms are reviewed. Measurements and calculations of total and Ps formation cross section ( QPs's) for positrons scattered by hydrogen atoms are in very good agreement, and for the most part there is also good agreement for sodium, potassium, and rubidium atoms, but there is a puzzling discrepancy between measured and recently calculated QPs's for sodium. Preliminary measurements of QPs's for Mg show a very rapid rise to a large maximum value less than 2 eV above the Ps formation threshold energy (0.8 eV) which may be related to the proximity of that threshold to zero energy. It appears that structure observed in e +-Ar and Kr QPs measurements may be related to capture of inner-subshell electrons.

  10. Alkali metal compatibility testing of candidate heater head materials for a Stirling engine heat transport system

    NASA Astrophysics Data System (ADS)

    Noble, Jack E.; Hickman, Gary L.; Grobstein, Toni

    The authors describe work performed as part of the 25-kWe advanced Stirling conversion system project. Liquid alkali metal compatibility is being assessed in an ongoing test program to evaluate candidate heater head materials and fabrication processes at the temperatures and operating conditions required for Stirling engines. Specific materials under evaluation are alloy 713LC, alloy 713LC coated with nickel aluminide, and Udimet 720, each in combination with Waspaloy. The tests were run at a constant 700 C. A eutectic alloy of sodium and potassium (NaK) was the working fluid. Titanium sheet in the system was shown to be an effective oxygen getter. Metallographic and microchemical examination of material surfaces, joints, and their interfaces revealed little or no corrosion after 1000 h. Tests are in progress, with up to 10,000 h exposure.

  11. Structure of the ambient temperature alkali metal molten salt AlCl3/LiSCN

    NASA Astrophysics Data System (ADS)

    Lee, Yi-Chia; Price, David L.; Curtiss, Larry A.; Ratner, Mark A.; Shriver, Duward F.

    2001-03-01

    The structure of the ambient temperature alkali metal molten salt system LiSCN/AlCl3 1:1 adduct was investigated by neutron diffraction, which demonstrates that the aluminum atom is surrounded by three chlorine atoms and one nitrogen atom, indicating the existence of the AlCl3NCS- anion, in which the NCS- coordinates to the Al center through nitrogen. Molecular orbital calculations using ab initio methods are also performed to study the optimized structures of the AlCl3NCS- and its isomer, AlCl3SCN-. The results are consistent with the neutron diffraction data and indicate that AlCl3NCS- is the major anionic complex in the 1:1 LiSCN/AlCl3 adduct.

  12. H-1 NMR study of ternary ammonia-alkali metal-graphite intercalation compounds

    NASA Technical Reports Server (NTRS)

    Tsang, T.; Fronko, R. M.; Resing, H. A.; Qian, X. W.; Solin, S. A.

    1987-01-01

    For the first-stage ternary ammonia-alkali metal-graphite intercalation compounds M(NH3)(x)C24(x of about 4, M = K, Rb, Cs), three sets of triplet H-1 NMR spectral lines have been observed at various temperatures and orientations due to the H-1 - H-1 and N-14 - H-1 dipolar interactions. The structures of these compounds have been inferred as mobile (liquid-like) intercalant layers of planar M(NH3)4 ions in between the carbon layers. For the intercalated ammonia molecules, the potential barrier is about 0.2 eV and the molecular geometry is very close to the free NH3 in gas phase.

  13. The alkali metal thermoelectric converter /AMTEC/ - A new direct energy conversion technology for aerospace power

    NASA Technical Reports Server (NTRS)

    Bankston, C. P.; Cole, T.; Jones, R.; Ewell, R.

    1982-01-01

    A thermally regenerative electrochemical device for the direct conversion of heat to electrical energy, the alkali metal thermoelectric converter (AMTEC), is characterized by potential efficiencies on the order of 15-40% and possesses no moving parts, making it a candidate for space power system applications. Device conversion efficiency is projected on the basis of experimental voltage vs current curves exhibiting power densities of 0.7 W/sq cm and measured electrode efficiencies of up to 40%. Preliminary radiative heat transfer measurements presented may be used in an investigation of methods for the reduction of AMTEC parasitic radiation losses. AMTEC assumes heat input and rejection temperatures of 900-1300 K and 400-800 K, respectively. The working fluid is liquid sodium, and the porous electrode employed is of molybdenum.

  14. Thermal characterization of an AMTEC recirculating test cell. [Alkali Metal ThermoElectric Converter

    NASA Technical Reports Server (NTRS)

    Underwood, M. L.; O'Connor, D.; Williams, R. M.; Jeffries-Nakamura, B.; Ryan, M. A.; Bankston, C. P.

    1990-01-01

    An alkali metal thermoelectric converter (AMTEC) recirculating test cell has been operated in order to determine the magnitudes of the primary heat losses of the cell and the value of the emissivity of the condenser surface. The energy balance included radiation losses, conductive losses, and losses due to the flow of sodium into the cell. The radiative heat flux dominated the heat loss mechanism of the cell at open circuit, and the condenser emissivity was calculated to be about 0.1. It is shown that, if this emissivity can be reduced to 0.02, then parasitic losses in an AMTEC recirculating test cell operating near peak power would be less than 40 percent of the heat required by the cell. The condenser emissivity decreases with elapsed time, resulting in improved thermal performance of the cell.

  15. Alkali metal compatibility testing of candidate heater head materials for a Stirling engine heat transport system

    NASA Technical Reports Server (NTRS)

    Noble, Jack E.; Hickman, Gary L.; Grobstein, Toni

    1991-01-01

    The authors describe work performed as part of the 25-kWe advanced Stirling conversion system project. Liquid alkali metal compatibility is being assessed in an ongoing test program to evaluate candidate heater head materials and fabrication processes at the temperatures and operating conditions required for Stirling engines. Specific materials under evaluation are alloy 713LC, alloy 713LC coated with nickel aluminide, and Udimet 720, each in combination with Waspaloy. The tests were run at a constant 700 C. A eutectic alloy of sodium and potassium (NaK) was the working fluid. Titanium sheet in the system was shown to be an effective oxygen getter. Metallographic and microchemical examination of material surfaces, joints, and their interfaces revealed little or no corrosion after 1000 h. Tests are in progress, with up to 10,000 h exposure.

  16. Sputtering and secondary ion emission properties of alkali metal films and adsorbed monolayers

    SciTech Connect

    Krauss, A R; Gruen, D M

    1980-01-01

    The secondary ion emission of alkali metal adsorbed monlayer and multilayer films has been studied. Profiling with sub-monolayer resolution has been performed by Auger, x-ray photoemission and secondary ion mass spectroscopy. Characteristic differences in the sputtering yields, and ion fraction have been observed which are associated with both the surface bonding properties and the mechanism leading to the formation of secondary ions. By sputtering with a negative bias applied to the sample, positive secondary ions are returned to the surface, resulting in a reduced sputter-induced erosion rate. Comparison with the results obtained with K and Li overlayers sputtered without sample bias provides an experimental value of both the total and secondary ion sputtering yields. The first and second monolayers can be readily identified and the first monolayer exhibits a lower sputtering yield and higher secondary ion fraction. This result is related to adsorption theory and measured values are compared with those obtained by thermal desorption measurements.

  17. Laboratory studies of alkali metal filter deposition, ultraviolet transmission, and visible blocking.

    PubMed

    Clarke, J T; Skinner, W R; Vincent, M B; Irgang, T; Suratkal, V; Grassl, H; Trauger, J T

    1999-03-20

    Far-ultraviolet alkali metal or Wood's filters have been produced and tested supporting the production of a flight filter for the Wide Field Planetary Camera 2 on the Hubble Space Telescope. Sodium layers 0.5-1-microm thick transmit up to 40% in the ultraviolet while efficiently blocking visible wavelengths. The prevention of visible pinholes is assisted by a clean, sleek-free surface and a cooled substrate during deposition. The coatings are stabilized efficiently by a bismuth overcoating whose transmission spectrum is presented. We also report for the first time, to our knowledge, the first demonstrated long-wavelength cutoff from a lithium filter, with a shorter cutoff wavelength than sodium and potentially higher stability for astronomical imaging. PMID:18305811

  18. Voltammetric studies of porous molybdenum electrodes for the alkali metal thermoelectric converter

    NASA Technical Reports Server (NTRS)

    Williams, R. M.; Bankston, C. P.; Khanna, S. K.; Cole, T.

    1986-01-01

    Voltammetry of partially oxidized porous molybdenum alkali metal thermoelectric converter (AMTEC) electrodes from about 600 to 1000 K revealed a series of redox processes within the AMTEC operational voltage range which can be used to establish the electronic and ionic conductivities of these electrodes. Improved estimates of the free energies of formation of Na2Mo3O6, NaMoO2, and Na3MoO4 are obtained. Evidence is provided for the slow corrosive attack by Na2MoO4 on molybdenum. The ionic conductivity of Na2MoO4 is found to be sufficiently large at temperatures of greater than 700 K to explain the observed electrochemical phenomena in addition to the enhanced sodium transport in AMTEC electrodes below the freezing point of Na2MoO4.

  19. PROCESS OF REMOVING PLUTONIUM VALUES FROM SOLUTION WITH GROUP IVB METAL PHOSPHO-SILICATE COMPOSITIONS

    DOEpatents

    Russell, E.R.; Adamson, A.W.; Schubert, J.; Boyd, G.E.

    1957-10-29

    A process for separating plutonium values from aqueous solutions which contain the plutonium in minute concentrations is described. These values can be removed from an aqueous solution by taking an aqueous solution containing a salt of zirconium, titanium, hafnium or thorium, adding an aqueous solution of silicate and phosphoric acid anions to the metal salt solution, and separating, washing and drying the precipitate which forms when the two solutions are mixed. The aqueous plutonium containing solution is then acidified and passed over the above described precipi-tate causing the plutonium values to be adsorbed by the precipitate.

  20. Magnetic Slowing Down of Spin Relaxation due to Binary Collisions of Alkali-Metal Atoms with Buffer-Gas Atoms

    NASA Astrophysics Data System (ADS)

    Walter, D. K.; Griffith, W. M.; Happer, W.

    2002-03-01

    We report the first studies of magnetic decoupling of the spin relaxation of alkali-metal atoms due to binary collisions with buffer gases. When binary collisions are the dominant relaxation mechanism, the relaxation and its magnetic decoupling are well described by the S-damping rate ΓSD due to the spin-rotation interaction γN˙S, the spin exchange rate ΓEX for collisions between alkali atoms, and a new ``Carver rate'' ΓC, due to the pressure-shift interaction δAİS, which can substantially broaden the magnetic decoupling curve while having no influence on the zero-field rates.

  1. Alkali metal vapor removal from pressurized fluidized-bed combustor flue gas. Quarterly report, October-December 1979

    SciTech Connect

    Johnson, I.; Swift, W.M.; Lee, S.H.D.; Jonke, A.A.

    1980-07-01

    This work supports the program to develop methods for the cleanup of combustion gases from pressurized fluidized-bed coal combustors so that the cleaned gases can be used for downstream gas turbines. This report presents the results of studies to develop granular sorbents for removing gaseous alkali metal compounds from high-temperature high-pressure combustion gases. Activated bauxite, one of the sorbents found to be effective, can be reused after removal of the alkali compound by a water-leaching process. Results of testing of this leaching process are reported. An experimental appartus for testing sorbents at high pressure has been built; results of preliminary tests are reported.

  2. 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.

  3. Reduction experiment of FeO-bearing amorphous silicate: application to origin of metallic iron in GEMS

    SciTech Connect

    Matsuno, Junya; Tsuchiyama, Akira; Miyake, Akira; Noguchi, Ryo; Ichikawa, Satoshi

    2014-09-10

    Glass with embedded metal and sulfides (GEMS) are amorphous silicates included in anhydrous interplanetary dust particles (IDPs) and can provide information about material evolution in our early solar system. Several formation processes for GEMS have been proposed so far, but these theories are still being debated. To investigate a possible GEMS origin by reduction of interstellar silicates, we synthesized amorphous silicates with a mean GEMS composition and performed heating experiments in a reducing atmosphere. FeO-bearing amorphous silicates were heated at 923 K and 973 K for 3 hr, and at 1023 K for 1-48 hr at ambient pressure in a reducing atmosphere. Fe grains formed at the interface between the silicate and the reducing gas through a reduction. In contrast, TEM observations of natural GEMS show that metallic grains are uniformly embedded in amorphous silicates. Therefore, the present study suggests that metallic inclusions in GEMS could not form as reduction products and that other formation process such as condensation or irradiation are more likely.

  4. Metal-silicate Partitioning at High Pressure and Temperature: Experimental Methods and a Protocol to Suppress Highly Siderophile Element Inclusions.

    PubMed

    Bennett, Neil R; Brenan, James M; Fei, Yingwei

    2015-01-01

    Estimates of the primitive upper mantle (PUM) composition reveal a depletion in many of the siderophile (iron-loving) elements, thought to result from their extraction to the core during terrestrial accretion. Experiments to investigate the partitioning of these elements between metal and silicate melts suggest that the PUM composition is best matched if metal-silicate equilibrium occurred at high pressures and temperatures, in a deep magma ocean environment. The behavior of the most highly siderophile elements (HSEs) during this process however, has remained enigmatic. Silicate run-products from HSE solubility experiments are commonly contaminated by dispersed metal inclusions that hinder the measurement of element concentrations in the melt. The resulting uncertainty over the true solubility and metal-silicate partitioning of these elements has made it difficult to predict their expected depletion in PUM. Recently, several studies have employed changes to the experimental design used for high pressure and temperature solubility experiments in order to suppress the formation of metal inclusions. The addition of Au (Re, Os, Ir, Ru experiments) or elemental Si (Pt experiments) to the sample acts to alter either the geometry or rate of sample reduction respectively, in order to avoid transient metal oversaturation of the silicate melt. This contribution outlines procedures for using the piston-cylinder and multi-anvil apparatus to conduct solubility and metal-silicate partitioning experiments respectively. A protocol is also described for the synthesis of uncontaminated run-products from HSE solubility experiments in which the oxygen fugacity is similar to that during terrestrial core-formation. Time-resolved LA-ICP-MS spectra are presented as evidence for the absence of metal-inclusions in run-products from earlier studies, and also confirm that the technique may be extended to investigate Ru. Examples are also given of how these data may be applied. PMID:26132380

  5. Argon Partitioning Between Metal and Silicate Liquids in the Laser-Heated DAC to 25 GPa

    NASA Astrophysics Data System (ADS)

    Bouhifd, M. A.; Jephcoat, A. P.

    2003-12-01

    The accretion of the Earth from primordial material and its subsequent segregation into core and mantle are fundamental problems in terrestrial and solar system science. Many of the questions about the process, although well developed as model scenarios over the last few decades, are still open and much debated, and include, for example, whether the core is, or was, a reservoir for the noble (rare) gases. In the present study we use for the first time the laser-heated diamond-anvil cell (LHDAC) to study the Ar partitioning at high-pressure and temperature between metal and silicate liquids. Little work has been reported on noble gas partitioning at pressure since a single multi-anvil experiment to 10 GPa (Matsuda et al., 1993). We used either compacted glass powders simulating that of a model C1 chondrite and iron metal, or pure metal alloys (pure Fe, FeNiCo alloy, FeSi). Thermal insulation from the diamonds was achieved with solid argon as pressure medium. The samples were heated by a multimode YAG laser for an average of 15 minutes and temperatures were determined spectro-radiometrically with a fit to a grey-body Planck function. Samples recovered after the runs were analysed by electron microprobe with spatial resolution near 1 μ m. The argon melts by conductive heating from the molten sample dissolving into the metal/silicate melt. Preliminary results on Ar solubility at lower pressures show good agreement with data reported by White et al. (1986) for Ar solubility in sanidine (KAlSi3O8). With sanidine melt, Ar solubility increases up to around 5-6 GPa where it reaches about 2.5 wt%, and remains roughly constant to higher pressures, suggesting that a threshold concentration is reached. Similar behavior is observed for a mix of C1-chondrite composition and iron and the results imply that the solubility of Ar is intimately related to liquid structure at high pressure. We also present results on Ar solubility into pure silicate liquids of varying composition in

  6. Mineralogy of silicate inclusions of the Colomera IIE iron and crystallization of Cr-diopside and alkali feldspar from a partial melt

    NASA Astrophysics Data System (ADS)

    Takeda, Hiroshi; Hsu, Weibiao; Huss, Gary R.

    2003-06-01

    We studied the mineralogy, mineral chemistry, and compositions of 48 interior silicate inclusions and a large K-rich surface inclusion from the Colomera IIE iron meteorite. Common minerals in the interior silicate inclusions are Cr diopside and Na plagioclase (albite). They are often enclosed by or coexist with albitic glasses with excess silica and minor Fe-Mg components. This mineral assemblage is similar to the "andesitic" material found in the Caddo County IAB iron meteorite for which a partial melt origin has been proposed. The fairly uniform compositions of Cr diopside (Ca 44Mg 46Fe 10) and Na plagioclase (Or 2.5Ab 90.0An 7.5 to Or 3.5Ab 96.1An 0.4) in Colomera interior inclusions and the angular boundaries between minerals and metal suggest that diopside and plagioclase partially crystallized under near-equilibrium conditions from a common melt before emplacement into molten metal. The melt-crystal assemblage has been called "crystal mush." The bulk compositions of the individual composite inclusions form an array between the most diopside-rich inclusion and plagioclase. This is consistent only with a simple mechanical mixing relationship, not a magmatic evolution series. We propose a model in which partly molten metal and crystal mush were mixed together by impact on the IIE parent body. Other models involving impact melting of the chondritic source material followed by growth of diopside and plagioclase do not easily explain near equilibrium growth of diopside and Na plagioclase, followed by rapid cooling. In the K-rich surface inclusion, K feldspar, orthopyroxene, and olivine were found together with diopside for the first time. K feldspar (sanidine, Or 92.7Ab 7.2An 0.1 to Or 87.3Ab 11.0An 1.7) occurs in an irregular veinlike region in contact with large orthopyroxene crystals of nearly uniform composition (Ca 1.3Mg 80.5Fe 17.8 to Ca 3.1Mg 78.1Fe 18.9) and intruding into a relict olivine with deformed-oval shape. Silica and subrounded Cr diopside are

  7. Constraints on Ureilite Petrogenesis and Carbon-Metal-Silicate Equilibria on the UPB

    NASA Astrophysics Data System (ADS)

    Goodrich, C. A.; Holloway, J. R.

    1992-07-01

    The most important constraints on models of ureilite petrogenesis are 1) Ureilites have lost a basaltic complement (they are ultramafic, extremely depleted in plagiophile elements, enriched in HREE, and have negative Eu anomalies and superchondritic Ca/Al ratios). 2) Ureilites experienced long equilibration times at high T (indicated by coarse grain size, extreme homogeneity of core crystals, correlations between olivine and pyroxene compositions, and metamorphic-like textures), followed by rapid cooling (indicated by structural features of pyroxene and narrow reduction rims on olivine). 3) Ureilites are probably residues (based on mass balance) but partly crystallized from melts. 4) Ureilites are derived from a minimum of six reservoirs that were distinct in oxygen isotopic composition and did not equilibrate with one another (this is consistent with the observation that olivine and pyroxene cores do not show correlations of mg with MnO, Cr2O3, Sm/Eu or Lu/Eu). 5) There is a correlation between oxygen isotopic composition and mg ratio in ureilites. Similar correlations are observed for Allende chondrules and group means of H3-L3-LL3 chondrites (Fig. 1), and are argued to result from nebular processes [1]. 6) If graphite-metal-silicate-CO/CO2 equilibrium was established during melting, then mg ratios of ureilites were determined by depth because CCO redox reactions are strongly pressure-dependent. Cohenite-bearing metallic spherule inclusions in the silicates and euhedral shapes of large graphite crystals in low-shock ureilites have been taken as evidence of equilibrium. Olivine reduction rims, highly variable interstitial metal compositions, and a lack of correlation between mg and metal content argue against equilibrium. 7) Ureilites either lost a low melting-T metal fraction or gained a refractory-rich metal component. (they have high abundances of siderophile elements but show fractionation between [Os, Ir, W, Re] and [Ni, Ga, Ge, Au]). 8) Primordial noble

  8. The formation of Mg,Fe-silicates by reactions between amorphous magnesiosilica smoke particles and metallic iron nanograins with implications for comet silicate origins

    NASA Astrophysics Data System (ADS)

    Rietmeijer, Frans J. M.; Nuth, Joseph A.; Pun, Aurora

    2013-10-01

    This thermal annealing experiment at 1000 K for up to 167 h used a physical mixture of vapor phase-condensed magnesiosilica grains and metallic iron nanograins to test the hypothesis that a mixture of magnesiosilica grains and an Fe-source would lead to the formation of ferromagnesiosilica grains. This exploratory study found that coagulation and thermal annealing of amorphous magnesiosilica and metallic grains yielded ferromagnesiosilica grains with the Fe/(Fe + Mg) ratios in interplanetary dust particles. Furthermore, decomposition of brucite present in the condensed magnesiosilica grains was the source for water and the cause of different iron oxidation states, and the formation of amorphous Fe3+-ferrosilica, amorphous Fe3+-Mg, Fe-silicates, and magnesioferrite during thermal annealing. Fayalite and ferrosilite that formed from silica/FeO melts reacted with forsterite and enstatite to form Mg, Fe-silicates. The presence of iron in different oxidation states in extraterrestrial materials almost certainly requires active asteroid-like parent bodies. If so, the possible presence of trivalent Fe compounds in comet P/Halley suggests that Halley-type comets are a mixture of preserved presolar and processed solar nebula dust. The results from this thermal annealing experiment further suggest that the Fe-silicates detected in the impact-induced ejecta from comet 9P/Temple 1 might be of secondary origin and related to the impact experiment or to processing in a regolith.

  9. Chemically bonded phospho-silicate ceramics

    DOEpatents

    Wagh, Arun S.; Jeong, Seung Y.; Lohan, Dirk; Elizabeth, Anne

    2003-01-01

    A chemically bonded phospho-silicate ceramic formed by chemically reacting a monovalent alkali metal phosphate (or ammonium hydrogen phosphate) and a sparsely soluble oxide, with a sparsely soluble silicate in an aqueous solution. The monovalent alkali metal phosphate (or ammonium hydrogen phosphate) and sparsely soluble oxide are both in powder form and combined in a stochiometric molar ratio range of (0.5-1.5):1 to form a binder powder. Similarly, the sparsely soluble silicate is also in powder form and mixed with the binder powder to form a mixture. Water is added to the mixture to form a slurry. The water comprises 50% by weight of the powder mixture in said slurry. The slurry is allowed to harden. The resulting chemically bonded phospho-silicate ceramic exhibits high flexural strength, high compression strength, low porosity and permeability to water, has a definable and bio-compatible chemical composition, and is readily and easily colored to almost any desired shade or hue.

  10. Room temperature inorganic ``quasi-molten salts`` as alkali-metal electrolytes

    SciTech Connect

    Xu, K.; Zhang, S.; Angell, C.A.

    1996-11-01

    Room temperature inorganic liquids of high ionic conductivity have been prepared by reacting Lewis acid AlCl with sulfonyl chlorides. The mechanism is not clear at this time since a crystal structure study of the 1:1 complex with CH{sub 3}SO{sub 2}Cl (T{sub m} = 30 C) is not consistent with a simple chloride transfer to create AlClO{sub 4}{sup {minus}} anions. The liquid is in a state somewhere between ionic and molecular. A new term quasi-molten salt is adopted to describe this state. A comparably conducting liquid can be made using BCL{sub 3} in place of AlCl{sub 3}. Unlike their organic counterparts based on ammonium cations (e.g., pyridinium or imidazolium) which reduce in the presence of alkali metals, this inorganic class of cation shows great stability against electrochemical reduction (ca. {minus}1.0 V vs. Li{sup +}/Li), with the useful consequence that reversible lithium and sodium metal deposition/stripping can be supported. The electrochemical window for these quasi-salts with AlCl{sub 3} ranges up to 5.0 V, and their room temperature conductivities exceed 10{sup {minus}4} S/cm. They dissolve lithium and sodium tetrachloroaluminates up to mole fraction {approximately} 0.6 at 100 C and intermediate compositions are permanently stable at ambient. The resultant lithium or sodium salt solutions exhibit electrochemical windows of 4.5--5.0 V vs. Li{sup +}/Li or Na{sup +}/Na and show room temperature conductivities of 10{sup {minus}3.0}--10{sup {minus}2.5} S/cm. In preliminary charge/discharge tests, the cell Li/``quasi-ionic liquid electrolyte``/Li{sub 1+x}Mn{sub 2}O{sub 4} showed a discharge capacity of ca. 110 mAh/(g of cathode) and sustained 80% of the initial capacity after 60 cycles, indicating that these quasi-molten salt-based electrolytes are promising candidates for alkali-metal batteries.

  11. Alkali metal pool boiler life tests for a 25 kWe advanced Stirling conversion system

    NASA Astrophysics Data System (ADS)

    Anderson, W. G.; Rosenfeld, J. H.; Noble, J.

    The overall operating temperature and efficiency of solar-powered Stirling engines can be improved by adding an alkali metal pool boiler heat transport system to supply heat more uniformly to the heater head tubes. One issue with liquid metal pool boilers is unstable boiling. Stable boiling is obtained with an enhanced boiling surface containing nucleation sites that promote continuous boiling. Over longer time periods, it is possible that the boiling behavior of the system will change. An 800-h life test was conducted to verify that pool boiling with the chosen fluid/surface combination remains stable as the system ages. The apparatus uses NaK boiling on a - 100 + 140 stainless steel sintered porous layer, with the addition of a small amount of xenon. Pool boiling remained stable to the end of life test. The pool boiler life test included a total of 82 cold starts, to simulate startup each morning, and 60 warm restarts, to simulate cloud cover transients. The behavior of the cold and warm starts showed no significant changes during the life test. In the experiments, the fluid/surface combination provided stable, high-performance boiling at the operating temperature of 700 C. Based on these experiments, a pool boiler was designed for a full-scale 25-kWe Stirling system.

  12. Elucidating the magnetic and superconducting phases in the alkali metal intercalated iron chalcogenides

    NASA Astrophysics Data System (ADS)

    Wang, Meng; Yi, Ming; Tian, Wei; Bourret-Courchesne, Edith; Birgeneau, Robert J.

    2016-02-01

    The complex interdigitated phases have greatly frustrated attempts to document the basic features of the superconductivity in the alkali metal intercalated iron chalcogenides. Here, using elastic neutron scattering, energy-dispersive x-ray spectroscopy, and resistivity measurements, we elucidate the relations of these phases in RbxFeySe2 -zSz . We find (i) the iron content is crucial in stabilizing the stripe antiferromagnetic (AF) phase with rhombic iron vacancy order (y ≈1.5 ) , the block AF phase with √{5 }×√{5 } iron vacancy order (y ≈1.6 ) , and the iron vacancy-free phase (y ≈2 ) ; and (ii) the iron vacancy-free superconducting phase (z =0 ) evolves into an iron vacancy-free metallic phase with sulfur substitution (z >1.5 ) due to the progressive decrease of the electronic correlation strength. Both the stripe AF phase and the block AF phase are Mott insulators. The iron-rich compounds (y >1.6 ) undergo a first order transition from an iron vacancy disordered phase at high temperatures into the √{5 }×√{5 } iron vacancy ordered phase and the iron vacancy-free phase below Ts. Our data demonstrate that there are miscibility gaps between these three phases. The existence of the miscibility gaps in the iron content is a key to understanding the relationship between these complicated phases.

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

    NASA Astrophysics Data System (ADS)

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

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

  14. An extended basis set {ital ab} {ital initio} study of alkali metal cation--water clusters

    SciTech Connect

    Feller, D.; Glendening, E.D.; Woon, D.E.; Feyereisen, M.W.

    1995-09-01

    Ionic clusters comprised of a single alkali metal cation and up to eight water molecules were studied at the Hartree--Fock and correlated levels of theory using the correlation consistent sequence of basis sets. Estimates of the degree of convergence in the computed properties with respect to the complete basis set limit were facilitated by the underlying systematic manner in which the correlation consistent sets approach completeness. In favorable cases, improved property values could be obtained by fitting finite basis set results with a simple analytical expression in order to extrapolate to the complete basis set limit. The sensitivity of structures and binding energies were analyzed with regard to the inclusion of valence and core-valence correlation recovery at the MP2, MP4, and CCSD(T) levels of theory. The replacement of metal core electrons and the introduction of relativistic contributions via effective core potentials was compared to corresponding all-electron results. {copyright} {ital 1995} {ital American} {ital Institute} {ital of} {ital Physics}.

  15. Alkali and alkaline earth metallic (AAEM) species leaching and Cu(II) sorption by biochar.

    PubMed

    Li, Mi; Lou, Zhenjun; Wang, Yang; Liu, Qiang; Zhang, Yaping; Zhou, Jizhi; Qian, Guangren

    2015-01-01

    Alkali and alkaline earth metallic (AAEM) species water leaching and Cu(II) sorption by biochar prepared from two invasive plants, Spartina alterniflora (SA) and water hyacinth (WH), were explored in this work. Significant amounts of Na and K can be released (maximum leaching for Na 59.0 mg g(-1) and K 79.9 mg g(-1)) from SA and WH biochar when they are exposed to contact with water. Cu(II) removal by biochar is highly related with pyrolysis temperature and environmental pH with 600-700 °C and pH of 6 showing best performance (29.4 and 28.2 mg g(-1) for SA and WH biochar). Cu(II) sorption exerts negligible influence on Na/K/Mg leaching but clearly promotes the release of Ca. Biochars from these two plant species provide multiple benefits, including nutrient release (K), heavy metal immobilization as well as promoting the aggregation of soil particles (Ca) for soil amelioration. AAEM and Cu(II) equilibrium concentrations in sorption were analyzed by positive matrix factorization (PMF) to examine the factors underlying the leaching and sorption behavior of biochar. The identified factors can provide insightful understanding on experimental phenomena. PMID:25194478

  16. Alkali metal pool boiler life tests for a 25 kWe advanced Stirling conversion system

    NASA Technical Reports Server (NTRS)

    Anderson, W. G.; Rosenfeld, J. H.; Noble, J.

    1991-01-01

    The overall operating temperature and efficiency of solar-powered Stirling engines can be improved by adding an alkali metal pool boiler heat transport system to supply heat more uniformly to the heater head tubes. One issue with liquid metal pool boilers is unstable boiling. Stable boiling is obtained with an enhanced boiling surface containing nucleation sites that promote continuous boiling. Over longer time periods, it is possible that the boiling behavior of the system will change. An 800-h life test was conducted to verify that pool boiling with the chosen fluid/surface combination remains stable as the system ages. The apparatus uses NaK boiling on a - 100 + 140 stainless steel sintered porous layer, with the addition of a small amount of xenon. Pool boiling remained stable to the end of life test. The pool boiler life test included a total of 82 cold starts, to simulate startup each morning, and 60 warm restarts, to simulate cloud cover transients. The behavior of the cold and warm starts showed no significant changes during the life test. In the experiments, the fluid/surface combination provided stable, high-performance boiling at the operating temperature of 700 C. Based on these experiments, a pool boiler was designed for a full-scale 25-kWe Stirling system.

  17. Tetrazole-5-carboxylic acid based salts of earth alkali and transition metal cations.

    PubMed

    Hartdegen, Vera; Klapötke, Thomas M; Sproll, Stefan M

    2009-10-01

    The tetrazole-5-carboxylate anion was investigated as ligand for earth alkali metal and transition metal complexes. Therefore, the strontium 4a (*3 H(2)O, *2.75 H(2)O, *2.5 H(2)O), barium 4b (*3 H(2)O), copper 4c (*3.5 H(2)O, *4 H(2)O), manganese 4d (*4 H(2)O, *5 H(2)O), and silver tetrazol-5-carboxylate 4e (*1.56 H(2)O) were synthesized and characterized by vibrational spectroscopy (IR), and the crystal structures of 4a (*2.75 H(2)O, *2.5 H(2)O), 4b*3 H(2)O, 4c*4 H(2)O, and 4d*5 H(2)O were determined using single crystal X-ray diffraction. The thermal stability was investigated by DSC-measurements, and the sensitivity toward impact and friction was determined by BAM-standards. The copper, strontium, and barium tetrazole-5-carboxyate proved to be suitable thermal and physical stable colorants for pyrotechnic compositions. The crystal structure of the tetragonal modification of strontium tetrazole-5-carboxyate possesses channels along the c-axis, leading to a porous material. PMID:19780625

  18. Composition of the core from gallium metal-silicate partitioning experiments

    NASA Astrophysics Data System (ADS)

    Blanchard, I.; Badro, J.; Siebert, J.; Ryerson, F. J.

    2015-10-01

    Gallium concentration (normalized to CI chondrites) in the mantle is at the same level as that of lithophile elements with similar volatility, implying that there must be little to no gallium in Earth's core. Metal-silicate partitioning experiments, however, have shown that gallium is a moderately siderophile element and should be therefore depleted in the mantle by core formation. Moreover, gallium concentrations in the mantle (4 ppm) are too high to be only brought by the late veneer; and neither pressure, nor temperature, nor silicate composition has a large enough effect on gallium partitioning to make it lithophile. We therefore systematically investigated the effect of core composition (light element content) on the partitioning of gallium by carrying out metal-silicate partitioning experiments in a piston-cylinder press at 2 GPa between 1673 K and 2073 K. Four light elements (Si, O, S, C) were considered, and their effect was found to be sufficiently strong to make gallium lithophile. The partitioning of gallium was then modeled and parameterized as a function of pressure, temperature, redox and core composition. A continuous core formation model was used to track the evolution of gallium partitioning during core formation, for various magma ocean depths, geotherms, core light element contents, and magma ocean composition (redox) during accretion. The only model for which the final gallium concentration in the silicate Earth matched the observed value is the one involving a light-element rich core equilibrating in a FeO-rich deep magma ocean (>1300 km) with a final pressure of at least 50 GPa. More specifically, the incorporation of S and C in the core provided successful models only for concentrations that lie far beyond their allowable cosmochemical or geophysical limits, whereas realistic O and Si amounts (less than 5 wt.%) in the core provided successful models for magma oceans deeper that 1300 km. These results offer a strong argument for an O- and Si

  19. Constraints on core formation in Vesta from metal-silicate partitioning of siderophile elements

    NASA Astrophysics Data System (ADS)

    Steenstra, E. S.; Knibbe, J. S.; Rai, N.; van Westrenen, W.

    2016-03-01

    It is now widely accepted that the asteroid 4-Vesta has an Fe-rich metallic core, but the composition of the core and the conditions prevailing during core-mantle differentiation are poorly constrained. In light of new constraints on Vesta's geophysical and geochemical properties obtained by the DAWN mission, we have re-examined the conditions at which core-mantle differentiation in Vesta may have occurred by linking the estimated mantle depletions of siderophile elements P, Co, Ni, Cu, Ga, Ge, Mo and W in the vestan mantle to newly derived predictive equations for core-mantle partitioning of these elements. We extend the number of elements previously considered in geochemical modeling of vestan core formation and use published metal-silicate partitioning data obtained at low pressures to characterize the dependence of metal/silicate partition coefficients (D) on pressure, temperature, oxygen fugacity and composition of the silicate and metallic melt. In our modeling we implement newly derived mantle depletions of P, Co, Ni and Ga through analysis of published HED meteorite analyses and assess two contrasting bulk compositional models for Vesta. Modeling results using Monte Carlo simulations constrain vestan core formation to have occurred at mildly reducing conditions of approximately 2 log units below the iron-wüstite (IW) buffer (ΔIW = -2.05 ± 0.20) if the two most likely bulk compositions (binary mixtures of H + CM or H + CV chondritic meteorites) are considered, assuming a temperature range between 1725 and 1850 K and a sulfur-free pure Fe core. If the core is assumed to be sulfur-rich (15 wt.% S) as predicted by the latter bulk compositional models, observed depletions for all eight siderophile elements can be simultaneously satisfied at ΔIW = -2.35 ± 0.10 and 1725-1850 K for the H + CV bulk composition and ΔIW = -2.30 ± 0.15 and 1725-1850 K for the H + CM bulk composition. More reducing conditions are not consistent with the observed siderophile

  20. Adsorption of alkali and alkaline-earth metal atoms on the reconstructed graphene-like BN single sheet

    NASA Astrophysics Data System (ADS)

    Hao, Jun-Hua; Wang, Zheng-Jia; Wang, Yu-Fang; Yin, Yu-Hua; Jiang, Run; Jin, Qing-Hua

    2015-12-01

    A graphene-like BN single sheet with absorbed alkali and alkaline-earth metal atoms have been investigated by using a first-principles method within the framework of density functional theory (DFT). The electronic structure of BN sheet with adsorbed metal atoms is mainly determined by the metal electronic state which is near to the Fermi level owing to the wide band gap of pure BN sheet. So, we calculated the adsorption energy, charge transfer and work function after the metal adsorbed on BN sheet. We found that the interaction between the metal atoms and BN surface was very strong, and the stable adsorption site for all the adsorbed atoms concluded was high-coordination surface site (H-center) rather than the surface dangling bond sites from the perspective of simple bond-counting arguments. Our results indicate that the interaction of BN sheet with metal atoms could help in the development of metallic nanoscale devices.

  1. Effect of sorbed molecules on the resistivity of alkali metal-graphite intercalation compounds

    SciTech Connect

    Akuzawa, Noboru Kunihashi, Yoji; Sato, Yuki; Tsuchiya, Ken-ichi; Matsumoto, Rika

    2007-03-15

    Alkali metal-graphite intercalation compounds with the composition of MC{sub 24} (M=K, Rb, Cs) were prepared by heating a mixture of MC{sub 8} (saturated compound) and graphite sheet (Grafoil) at 350-450 deg. C. The resistivity perpendicular to the layer planes ({rho} {sub c}) of the resulting compounds was determined by the two-terminal method. The anisotropy factor of the resistivity, ({rho} {sub c}/{rho} {sub a}), of KC{sub 24} prepared from Grafoil was {approx}130, being about 1/6-1/10 in magnitude compared with that of KC{sub 24} prepared from highly oriented pyrolytic graphite. The resistivity change during sorption of hydrogen (at 90 K), ethylene (at 194 K) and acetylene (at 194 K) was determined. The resistivity of MC{sub 24} increased with increase of the sorbed amount of H{sub 2}. The magnitude of the increase was in the order KC{sub 24}>RbC{sub 24}>CsC{sub 24}. This resistivity increase was considered to be due to the expansion along c-direction which reduces the charge-transfer interaction between the carbon layers and potassium ions, resulting in the decrease of the density of the conduction electron. The resistivity of MC{sub 24} increased extensively during sorption of C{sub 2}H{sub 4} and C{sub 2}H{sub 2}. It was discussed in connection with the in-plane structural transition and chemical interaction between alkali metal ions and sorbed molecules. - Graphical abstract: The resistivity of MC{sub 24} increased with increase of the sorbed amount of H{sub 2}. The magnitude of the increase was in the order KC{sub 24}>RbC{sub 24}>CsC{sub 24}. This resistivity increase was considered to be due to the expansion along c-direction which reduces the charge-transfer interaction between the carbon layers and potassium ions.

  2. Negative ion production by backscattering from alkali-metal surfaces bombarded by ions of hydrogen and deuterium

    SciTech Connect

    Schneider, P.J.

    1980-03-01

    Measurements have been made of the total backscattered D/sup -/ and H/sup -/ yields from thick, clean targets of Cs, Rb, K, Na, and Li, bombarded with H/sub 2//sup +/, H/sub 3//sup +/, D/sub 2//sup +/, and D/sub 3//sup +/ with incident energies from 0.15 to 4.0 keV/nucleus. All of the measurements were made at background pressures less than 10/sup -9/ Torr and the alkali-metal targets were evaporated onto a cold substrate (T = 77K) in situ to assure thick, uncontaminated targets. Measurements of the H/sup -/ yield from various transition metal targets with thin coverages of alkali-metals have also been made as a function of the surface work function. The negative ion yields are discussed in terms of the probabilities of reflection of the incident particles, of formation of the negative ion at the surface and of the survival of the negative ion leaving the surface. For each thick alkali-metal target, the negative ion yield measurements have been used in a least squares fit to determine two parameters in a theoretically derived expression for the negative ion yield. The parameters obtained from a thick Na target have been used to calculate the yield from a Cu target with thin coverage of Na (such that the surface work function is equal to thick Na).

  3. Solid State Structures of Alkali Metal Ion Complexes Formed by Low-Molecular-Weight Ligands of Biological Relevance.

    PubMed

    Aoki, Katsuyuki; Murayama, Kazutaka; Hu, Ning-Hai

    2016-01-01

    This chapter provides structural data, mainly metal binding sites/modes, observed in crystal structures of alkali metal ion complexes containing low-molecular-weight ligands of biological relevance, mostly obtained from the Cambridge Structural Database (the CSD version 5.35 updated to February 2014). These ligands include (i) amino acids and small peptides, (ii) nucleic acid constituents (excluding quadruplexes and other oligonucleotides), (iii) simple carbohydrates, and (iv) naturally occurring antibiotic ionophores. For some representative complexes of these ligands, some details on the environment of the metal coordination and structural characteristics are described. PMID:26860299

  4. Preparation of decarboxylic-functionalized weak cation exchanger and application for simultaneous separation of alkali, alkaline earth and transition metals.

    PubMed

    Peng, Yahui; Gan, Yihui; He, Chengxia; Yang, Bingcheng; Guo, Zhimou; Liang, Xinmiao

    2016-06-01

    A novel weak cation exchanger (WCX) with dicarboxyl groups functionalized has been developed by clicking mercaptosuccinic acid onto silica gel. The simple synthesis starts with modification of silica gel with triethoxyvinylsilane, followed by efficient coupling vinyl-bonded silica with mercaptosuccinic acid via a "thiol-ene" click reaction. The obtained WCX demonstrated good separation and high selectivity towards common metals. Simultaneous separation of 10 alkali, alkaline earth and transition metals was achieved within 12min. Ion exchange and complex mechanism dominates the separation process. Its utility was demonstrated for determination of metals in tap water. PMID:27130093

  5. On the metallicity dependence of crystalline silicates in oxygen-rich asymptotic giant branch stars and red supergiants

    NASA Astrophysics Data System (ADS)

    Jones, O. C.; Kemper, F.; Sargent, B. A.; McDonald, I.; Gielen, C.; Woods, Paul M.; Sloan, G. C.; Boyer, M. L.; Zijlstra, A. A.; Clayton, G. C.; Kraemer, K. E.; Srinivasan, S.; Ruffle, P. M. E.

    2012-12-01

    We investigate the occurrence of crystalline silicates in oxygen-rich evolved stars across a range of metallicities and mass-loss rates. It has been suggested that the crystalline silicate feature strength increases with increasing mass-loss rate, implying a correlation between lattice structure and wind density. To test this, we analyse Spitzer Infrared Spectrograph and Infrared Space Observatory Short Wavelength Spectrometer spectra of 217 oxygen-rich asymptotic giant branch and 98 red supergiants in the Milky Way, the Large and Small Magellanic Clouds, and Galactic globular clusters. These encompass a range of spectral morphologies from the spectrally rich which exhibit a wealth of crystalline and amorphous silicate features to 'naked' (dust-free) stars. We combine spectroscopic and photometric observations with the GRAMS grid of radiative transfer models to derive (dust) mass-loss rates and temperature. We then measure the strength of the crystalline silicate bands at 23, 28 and 33 μm. We detect crystalline silicates in stars with dust mass-loss rates which span over 3 dex, down to rates of ˜10-9 M⊙ yr-1. Detections of crystalline silicates are more prevalent in higher mass-loss rate objects, though the highest mass-loss rate objects do not show the 23-μm feature, possibly due to the low temperature of the forsterite grains or it may indicate that the 23-μm band is going into absorption due to high column density. Furthermore, we detect a change in the crystalline silicate mineralogy with metallicity, with enstatite seen increasingly at low metallicity.

  6. New studies of optical pumping, spin resonances, and spin exchange in mixtures of inert gases and alkali-metal vapors

    NASA Astrophysics Data System (ADS)

    Jau, Yuan-Yu

    In this thesis, we present new studies of alkali-hyperfine resonances, new optical pumping of alkali-metal atoms, and the new measurements of binary spin-exchange cross-section between alkali-metal atoms and xenon atoms. We report a large light narrowing effect of the hyperfine end-resonance signals, which was predicted from our theory and observed in our experiments. By increasing the intensity of the circularly polarized pumping beam, alkali-metal atoms are optically pumped into a state of static polarization, and trapped into the hyperfine end-state. Spin exchange between alkali-metal atoms has minimal effect on the end-resonance of the highly spin-polarized atoms. This new result will possibly benefit the design of atomic clocks and magnetometer. We also studied the pressure dependence of the atomic-clock resonance linewidth and pointed out that the linewidth was overestimated by people in the community of atomic clock. Next, we present a series study of coherent population trapping (CPT), which is a promising technique with the same or better performance compared to the traditional microwave spectroscopy. For miniature atomic clocks, CPT method is thought to be particularly advantages. From our studies, we invented a new optical-pumping method, push-pull optical pumping, which can pump atoms into nearly pure 0-0 superposition state, the superposition state of the two ground-state hyperfine sublevels with azimuthal quantum number m = 0. We believe this new invention will bring a big advantage to CPT frequency standards, the quantum state preparation for cold atoms or hot vapor, etc. We also investigated the pressure dependence of CPT excitation and the line shape of the CPT resonance theoretically and experimentally. These two properties are important for CPT applications. A theoretical study of "photon cost" of optical pumping is also presented. Finally, we switch our attention to the problem of spin exchange between alkali-metal atoms and xenon gas. This

  7. The formation of silver metal nanoparticles by ion implantation in silicate glasses

    NASA Astrophysics Data System (ADS)

    Vytykacova, S.; Svecova, B.; Nekvindova, P.; Spirkova, J.; Mackova, A.; Miksova, R.; Böttger, R.

    2016-03-01

    It has been shown that glasses containing silver metal nanoparticles are promising photonics materials for the fabrication of all-optical components. The resulting optical properties of the nanocomposite glasses depend on the composition and structure of the glass, as well as on the type of metal ion implanted and the experimental procedures involved. The main aim of this article was to study the influence of the conditions of the ion implantation and the composition of the glass on the formation of metal nanoparticles in such glasses. Four various types of silicate glasses were implanted with Ag+ ions with different energy (330 keV, 1.2 MeV and 1.7 MeV), with the fluence being kept constant (1 × 1016 ions cm-2). The as-implanted samples were annealed at 600 °C for 1 h. The samples were characterised in terms of: the nucleation of metal nanoparticles (linear optical absorption), the migration of silver through the glass matrix during the implantation and post-implantation annealing (Rutherford backscattering spectroscopy), and the oxidation state of silver (photoluminescence in the visible region).

  8. In situ alkali-silica reaction observed by x-ray microscopy

    SciTech Connect

    Kurtis, K.E.; Monteiro, P.J.M.; Brown, J.T.; Meyer-Ilse, W.

    1997-04-01

    In concrete, alkali metal ions and hydroxyl ions contributed by the cement and reactive silicates present in aggregate can participate in a destructive alkali-silica reaction (ASR). This reaction of the alkalis with the silicates produces a gel that tends to imbibe water found in the concrete pores, leading to swelling of the gel and eventual cracking of the affected concrete member. Over 104 cases of alkali-aggregate reaction in dams and spillways have been reported around the world. At present, no method exists to arrest the expansive chemical reaction which generates significant distress in the affected structures. Most existing techniques available for the examination of concrete microstructure, including ASR products, demand that samples be dried and exposed to high pressure during the observation period. These sample preparation requirements present a major disadvantage for the study of alkali-silica reaction. Given the nature of the reaction and the affect of water on its products, it is likely that the removal of water will affect the morphology, creating artifacts in the sample. The purpose of this research is to observe and characterize the alkali-silica reaction, including each of the specific reactions identified previously, in situ without introducing sample artifacts. For observation of unconditioned samples, x-ray microscopy offers an opportunity for such an examination of the alkali-silica reaction. Currently, this investigation is focusing on the effect of calcium ions on the alkali-silica reaction.

  9. Alkali metal vapor removal from pressurized fluidized-bed combustor flue gas. Annual report, October 1979-September 1980

    SciTech Connect

    Johnson, I.; Swift, W.M.; Lee, S.H.D.

    1980-10-01

    In the application of pressurized fluidized-bed combustion (PFBC) to the generation of electricity, hot corrosion of the gas turbine (downstream from the combustor) by alkali metal compounds is a potential problem. The objective of this investigation is to develop a method for the removal of gaseous alkali metal compounds from the high-pressure high-temperature gas from a PFBC before the gas enters the gas turbine. The use of a granular bed filter, with either diatomaceous earth or activated bauxite as the bed material, is under study. Breakthrough data are reported on the sorption of gaseous NaCl by activated bauxite. Results are reported for the regeneration of activated bauxite using water leaching and a thermal swing method.

  10. Ground state of the polar alkali-metal-atom-strontium molecules: Potential energy curve and permanent dipole moment

    SciTech Connect

    Guerout, R.; Aymar, M.; Dulieu, O.

    2010-10-15

    In this study, we investigate the structure of the polar alkali-metal-atom-strontium diatomic molecules as possible candidates for the realization of samples of ultracold polar molecular species not yet investigated experimentally. Using a quantum chemistry approach based on effective core potentials and core polarization potentials, we model these systems as effective three-valence-electron systems, allowing for calculation of electronic properties with full configuration interaction. The potential curve and the permanent dipole moment of the {sup 2}{Sigma}{sup +} ground state are determined as functions of the internuclear distance for LiSr, NaSr, KSr, RbSr, and CsSr molecules. These molecules are found to exhibit a significant permanent dipole moment, though smaller than those of the alkali-metal-atom-Rb molecules.

  11. The relationship between molecular structure and biological activity of alkali metal salts of vanillic acid: Spectroscopic, theoretical and microbiological studies

    NASA Astrophysics Data System (ADS)

    Świsłocka, Renata; Piekut, Jolanta; Lewandowski, Włodzimierz

    In this paper we investigate the relationship between molecular structure of alkali metal vanillate molecules and their antimicrobial activity. To this end FT-IR, FT-Raman, UV absorption and 1H, 13C NMR spectra for lithium, sodium, potassium, rubidium and caesium vanillates in solid state were registered, assigned and analyzed. Microbial activity of studied compounds was tested against Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, Proteus vulgaris, Bacillus subtilis and Candida albicans. In order to evaluate the dependence between chemical structure and biological activity of alkali metal vanillates the statistical analysis was performed for selected wavenumbers from FT-IR spectra and parameters describing microbial activity of vanillates. The geometrical structures of the compounds studied were optimized and the structural characteristics were determined by density functional theory (DFT) using at B3LYP method with 6-311++G** as basis set. The obtained statistical equations show the existence of correlation between molecular structure of vanillates and their biological properties.

  12. Characterization of Adsorbed Alkali Metal Ions in 2:1 Type Clay Minerals from First-Principles Metadynamics.

    PubMed

    Ikeda, Takashi; Suzuki, Shinichi; Yaita, Tsuyoshi

    2015-07-30

    Adsorption states of alkali metal ions in three kinds of 2:1 type clay minerals are systematically investigated via first-principles-based metadynamics. Our reconstructed free energy surfaces in a two-dimensional space of coordination numbers specifically employed as collective variables for describing the interlayer cations show that an inner-sphere (IS) complex is preferentially formed for Cs(+) in the 2:1 type trioctahedral clay minerals with saponite-like compositions, where lighter alkali metal ions show a tendency to form an outer-sphere one instead. The strong preference for an IS complex observed for Cs(+) is found to result partially from the capability of recognizing selectively Cs(+) ions at the basal O atoms with the Lewis basicity significantly enhanced by the isomorphic substitution in tetrahedral sheets. PMID:26151150

  13. Research Investigation Directed Toward Extending the Useful Range of the Electromagnetic Spectrum. [atomic spectra and electronic structure of alkali metals

    NASA Technical Reports Server (NTRS)

    Hartmann, S. R.; Happer, W.

    1974-01-01

    The report discusses completed and proposed research in atomic and molecular physics conducted at the Columbia Radiation Laboratory from July 1972 to June 1973. Central topics described include the atomic spectra and electronic structure of alkali metals and helium, molecular microwave spectroscopy, the resonance physics of photon echoes in some solid state systems (including Raman echoes, superradiance, and two photon absorption), and liquid helium superfluidity.

  14. Alkali-vapor cell with metal coated windows for efficient application of an electric field

    NASA Astrophysics Data System (ADS)

    Sarkisyan, D.; Sarkisyan, A. S.; Guéna, J.; Lintz, M.; Bouchiat, M.-A.

    2005-05-01

    We describe the implementation of a cylindrical T-shaped alkali-vapor cell for laser spectroscopy in the presence of a longitudinal electric field. The two windows are used as two electrodes of the high-voltage assembly, which is made possible by a metallic coating which entirely covers the inner and outer sides of the windows except for a central area to let the laser beams in and out of the cell. This allows very efficient application of the electric field, up to 2kV/cm in a rather dense superheated vapor, even when significant photoemission takes place at the windows during pulsed laser irradiation. The body of the cell is made of sapphire or alumina ceramic to prevent large currents resulting from surface conduction observed in cesiated glass cells. The technique used to attach the monocrystalline sapphire windows to the cell body causes minimal stress birefringence in the windows. In addition, reflection losses at the windows can be made very small. The vapor cell operates with no buffer gas and has no magnetic part. The use of this kind of cell has resulted in an improvement of the signal-to-noise ratio in the measurement of parity violation in cesium vapor underway at ENS, Paris. The technique can be applied to other situations where a brazed assembly would give rise to unacceptably large birefringence in the windows.

  15. A novel alkali metals/strontium co-substituted calcium polyphosphate scaffolds in bone tissue engineering.

    PubMed

    Song, Wei; Wang, Qiguang; Wan, Changxiu; Shi, Tong; Markel, David; Blaiser, Ralph; Ren, Weiping

    2011-08-01

    Our purpose of this study is to develop potassium or sodium/strontium co-substituted calcium polyphosphate (K/Sr-CPP or Na/Sr-CPP) bioceramics in application of bone repairing scaffold. The incorporation of K, Na, and Sr into CPP substrate via a calcining-sintering process was confirmed by X-ray diffractometry and inductively coupled plasma atomic emission spectroscopy. In vitro degradation study of co-substituted CPP indicated the incorporation of alkali metal elements promoted the degradability of CPP, and the scanning electron microscope showed the apatite-like minerals were precipitated on the surface of co-substituted CPP. The compress resistant strength of co-substituted CPP was elevated by dopants. The MTT assay and confocal laser-scanning microscope on osteoblasts culturing with co-substituted CPP showed no cytotoxicity. The cell proliferation on co-substituted CPP was even better than others. Thus, this co-substituted CPP bioceramics might have potential of applications in orthopedic field. PMID:21732528

  16. Alkali Metal Cation versus Proton and Methyl Cation Affinities: Structure and Bonding Mechanism

    PubMed Central

    Boughlala, Zakaria; Fonseca Guerra, Célia

    2016-01-01

    Abstract We have analyzed the structure and bonding of gas‐phase Cl−X and [HCl−X]+ complexes for X+= H+, CH3 +, Li+, and Na+, using relativistic density functional theory (DFT). We wish to establish a quantitative trend in affinities of the anionic and neutral Lewis bases Cl− and HCl for the various cations. The Cl−X bond becomes longer and weaker along X+ = H+, CH3 +, Li+, and Na+. Our main purpose is to understand the heterolytic bonding mechanism behind the intrinsic (i.e., in the absence of solvent) alkali metal cation affinities (AMCA) and how this compares with and differs from those of the proton affinity (PA) and methyl cation affinity (MCA). Our analyses are based on Kohn–Sham molecular orbital (KS‐MO) theory in combination with a quantitative energy decomposition analysis (EDA) that pinpoints the importance of the different features in the bonding mechanism. Orbital overlap appears to play an important role in determining the trend in cation affinities. PMID:27551660

  17. Silicon halide-alkali metal flames as a source of solar grade silicon

    NASA Technical Reports Server (NTRS)

    Olson, D. B.; Miller, W. J.; Gould, R. K.

    1980-01-01

    The feasibility of using continuous high-temperature reactions of alkali metals and silicon halides to produce silicon in large quantities and of suitable purity for use in the production of photovoltaic solar cells was demonstrated. Low pressure experiments were performed demonstrating the production of free silicon and providing experience with the construction of reactant vapor generators. Further experiments at higher reagent flow rates were performed in a low temperature flow tube configuration with co-axial injection of reagents and relatively pure silicon was produced. A high temperature graphite flow tube was built and continuous separation of Si from NaCl was demonstrated. A larger scaled well stirred reactor was built. Experiments were performed to investigate the compatability of graphite based reactor materials of construction with sodium. At 1100 to 1200 K none of these materials were found to be suitable. At 1700 K the graphites performed well with little damage except to coatings of pyrolytic graphite and silicon carbide which were damaged.

  18. Stable Alkali-Metal Complexes of Hybrid Disila-Crown Ethers.

    PubMed

    Reuter, Kirsten; Buchner, Magnus R; Thiele, Günther; von Hänisch, Carsten

    2016-05-01

    The complexation ability of hybrid disilane and ethylene containing crown ether ring systems was analyzed using 1,2-disila[12]crown-4 (1), 1,2-disila[15]crown-5 (2), 1,2-disila[18]crown-6 (3), and 1,2,7,8-tetrasila[12]crown-4 (7). Alkali-metal complexes (Li(+), Na(+), K(+)) were obtained and analyzed via X-ray diffraction. The complex stability of [Li(1,2-disila[12]crown-4)](+) and [Li(1,2,7,8-tetrasila[12]crown-4)](+) was determined, in relation to the lithium complex of [12]crown-4, by density functional theory (DFT) calculations employing the BP86/def2-TZVP level of theory. In solution, the exchange of lithium cations between pure [12]crown-4 and hybrid [12]crown-4 is on even terms, as has been shown from the relative binding affinity of compounds 1 and 7 by means of dynamic proton nuclear magnetic resonance (NMR) spectroscopy. PMID:27082743

  19. Interaction of alkali metals with perylene-3,4,9,10- tetracarboxylic-dianhydride thin films

    SciTech Connect

    Wuesten, J.; Berger, S.; Heimer, K.; Lach, S.; Ziegler, Ch.

    2005-07-01

    n doping of the molecular organic semiconductor perylene-3,4,9,10-tetracarboxylic-dianhydride (PTCDA) is often achieved by use of alkali metals as dopants. This doping process is commonly performed in two steps. In the first the dopant is evaporated onto the surface of the PTCDA film. As it has been believed that the dopant shows an inhomogeneous diffusion profile through the layer with most of the dopant accumulated in the first few layers, a subsequent annealing step has been performed in order to reach a homogeneous distribution of the dopant in the whole layer. In this paper experimental results concerning chemical composition ((angle resolved) X-ray photoemission spectroscopy, secondary-ion-mass spectrometry, Fourier transform infrared spectroscopy), electronic structure (ultraviolet photoemission spectroscopy, inverse photoemission spectroscopy), as well as electrical properties (conductivity, Seebeck coefficient) are shown before and after doping and before and after annealing. These results suggest that the deposited dopant is redistributed and partially removed during the annealing step. A model for the dopant distribution is suggested.

  20. Atomic many-body effects and Lamb shifts in alkali metals

    NASA Astrophysics Data System (ADS)

    Ginges, J. S. M.; Berengut, J. C.

    2016-05-01

    We present a detailed study of the radiative potential method [V. V. Flambaum and J. S. M. Ginges, Phys. Rev. A 72, 052115 (2005), 10.1103/PhysRevA.72.052115], which enables the accurate inclusion of quantum electrodynamics (QED) radiative corrections in a simple manner in atoms and ions over the range 10 ≤Z ≤120 , where Z is the nuclear charge. Calculations are performed for binding energy shifts to the lowest valence s , p , and d waves over the series of alkali-metal atoms Na to E119. The high accuracy of the radiative potential method is demonstrated by comparison with rigorous QED calculations in frozen atomic potentials, with deviations on the level of 1%. The many-body effects of core relaxation and second- and higher-order perturbation theory on the interaction of the valence electron with the core are calculated. The inclusion of many-body effects tends to increase the size of the shifts, with the enhancement particularly significant for d waves; for K to E119, the self-energy shifts for d waves are only an order of magnitude smaller than the s -wave shifts. It is shown that taking into account many-body effects is essential for an accurate description of the Lamb shift.

  1. Alkali Metal Cation versus Proton and Methyl Cation Affinities: Structure and Bonding Mechanism.

    PubMed

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

    2016-06-01

    We have analyzed the structure and bonding of gas-phase Cl-X and [HCl-X](+) complexes for X(+)= H(+), CH3 (+), Li(+), and Na(+), using relativistic density functional theory (DFT). We wish to establish a quantitative trend in affinities of the anionic and neutral Lewis bases Cl(-) and HCl for the various cations. The Cl-X bond becomes longer and weaker along X(+) = H(+), CH3 (+), Li(+), and Na(+). Our main purpose is to understand the heterolytic bonding mechanism behind the intrinsic (i.e., in the absence of solvent) alkali metal cation affinities (AMCA) and how this compares with and differs from those of the proton affinity (PA) and methyl cation affinity (MCA). Our analyses are based on Kohn-Sham molecular orbital (KS-MO) theory in combination with a quantitative energy decomposition analysis (EDA) that pinpoints the importance of the different features in the bonding mechanism. Orbital overlap appears to play an important role in determining the trend in cation affinities. PMID:27551660

  2. Partitioning of transition metals between diopside and coexisting silicate liquids. I - Nickel, cobalt, and manganese

    NASA Technical Reports Server (NTRS)

    Lindstrom, D. J.; Weill, D. F.

    1978-01-01

    Distribution coefficients have been found for the partitioning of Ni, Co, and Mn between calcium-rich clinopyroxenes and coexisting silicate liquids. Values are found for the 1110-1360 C temperature range. The breakdown of Henry's Law was not observed. The measured clinopyroxene/liquid distribution coefficients ranged from 1.5-14.0 for Ni, 0.5-2.0 for Co, and 0.3-1.2 for Mn. Analyses of pyroxenes grown from charges differing in the amounts of transition metals indicate that Ni and Co occupy the M1 site of diopside and that Mn occupies the M1 and M2 sites. Equilibrium constants were found in terms of the activities of the components in the liquid and solid phases. These activities are based on the mole fractions. An activity/concentration model was used for the liquid phase in order to explain the variations in the clinopyroxene/liquid coefficients due to bulk composition.

  3. Properties of alkali metal atoms deposited on a MgO surface: a systematic experimental and theoretical study.

    PubMed

    Finazzi, Emanuele; Di Valentin, Cristiana; Pacchioni, Gianfranco; Chiesa, Mario; Giamello, Elio; Gao, Hongjun; Lian, Jichun; Risse, Thomas; Freund, Hans-Joachim

    2008-01-01

    The adsorption of small amounts of alkali metal atoms (Li, Na, K, Rb, and Cs) on the surface of MgO powders and thin films has been studied by means of EPR spectroscopy and DFT calculations. From a comparison of the measured and computed g values and hyperfine coupling constants (hfccs), a tentative assignment of the preferred adsorption sites is proposed. All atoms bind preferentially to surface oxide anions, but the location of these anions differs as a function of the deposition temperature and alkali metal. Lithium forms relatively strong bonds with MgO and can be stabilized at low temperatures on terrace sites. Potassium interacts very weakly with MgO and is stabilized only at specific sites, such as at reverse corners where it can interact simultaneously with three surface oxygen atoms (rubidium and cesium presumably behave in the same way). Sodium forms bonds of intermediate strength and could, in principle, populate more than a single site when deposited at room temperature. In all cases, large deviations of the hfccs from the gas-phase values are observed. These reductions in the hfccs are due to polarization effects and are not connected to ionization of the alkali metal, which would lead to the formation of an adsorbed cation and a trapped electron. In this respect, hydrogen atoms behave completely differently. Under similar conditions, they form (H(+))(e(-)) pairs. The reasons for this different behavior are discussed. PMID:18381711

  4. Element specificity of ortho-positronium annihilation for alkali-metal loaded SiO{sub 2} glasses

    SciTech Connect

    Sato, K.; Hatta, T.

    2015-03-07

    Momentum distributions associated with ortho-positronium (o-Ps) pick-off annihilation photon are often influenced by light elements, as, e.g., carbon, oxygen, and fluorine. This phenomenon, so-called element specificity of o-Ps pick-off annihilation, has been utilized for studying the elemental environment around the open spaces. To gain an insight into the element specificity of o-Ps pick-off annihilation, the chemical shift of oxygen 1s binding energy and the momentum distributions associated with o-Ps pick-off annihilation were systematically investigated for alkali-metal loaded SiO{sub 2} glasses by means of X-ray photoelectron spectroscopy and positron-age-momentum correlation spectroscopy, respectively. Alkali metals introduced into the open spaces surrounded by oxygen atoms cause charge transfer from alkali metals to oxygen atoms, leading to the lower chemical shift for the oxygen 1s binding energy. The momentum distribution of o-Ps localized into the open spaces is found to be closely correlated with the oxygen 1s chemical shift. This correlation with the deepest 1s energy level evidences that the element specificity of o-Ps originates from pick-off annihilation with orbital electrons, i.e., dominantly with oxygen 2p valence electrons and s electrons with lower probability.

  5. Iron-catalysed propylene epoxidation by nitrous oxide: dramatic shift of allylic oxidation to epoxidation by the modification with alkali metal salts.

    PubMed

    Wang, Xiaoxing; Zhang, Qinghong; Guo, Qian; Lou, Yinchuan; Yang, Lujuan; Wang, Ye

    2004-06-21

    A dramatic shift of allylic oxidation to epoxidation has been observed during the oxidation of propylene by N(2)O when the FeO(x)/SBA-15 catalyst is modified with alkali metal salts, and the roles of alkali metal salts are to suppress the reactivity of lattice oxygen and to induce an iron coordination structure effective for epoxidation with N(2)O. PMID:15179482

  6. Structure of glasses containing transition metal ions. Progress report, February 1, 1979-January 31, 1980

    SciTech Connect

    White, W B; Furukawa, T; Tsong, I S.T.; Fox, K; Herman, J S; Houser, C; Nelson, C

    1980-02-01

    New normal coordinate calculations were used to relate the vibrational frequencies of silicate glasses to Si-O force constants. These appear to account for the observed frequency shifts with degree of silica polymerization. Raman spectroscopy has been used to elucidate the structure of sodium borosilicate glasses and of sodium aluminosilicate glasses. Structures of compositionally complex glasses can be understood if spectra are measured on many glasses spaced at small compositional intervals. Optical absorption spectra were used to investigate the structural setting of iron in alkali silicate glasses. Research on the alkali-hydrogen exchange in alkali silicate glasses was completed and additional work on ternary glasses is under way. A series of appendices present completed work on the structural investigations of alkali borosilicate glasses, on the structural setting of transition metal ions in glasses, and on the diffusion of hydrogen in alkali silicate glasses.

  7. Metal and Silicate Particles Including Nanoparticles Are Present in Electronic Cigarette Cartomizer Fluid and Aerosol

    PubMed Central

    Williams, Monique; Villarreal, Amanda; Bozhilov, Krassimir; Lin, Sabrina; Talbot, Prue

    2013-01-01

    Background Electronic cigarettes (EC) deliver aerosol by heating fluid containing nicotine. Cartomizer EC combine the fluid chamber and heating element in a single unit. Because EC do not burn tobacco, they may be safer than conventional cigarettes. Their use is rapidly increasing worldwide with little prior testing of their aerosol. Objectives We tested the hypothesis that EC aerosol contains metals derived from various components in EC. Methods Cartomizer contents and aerosols were analyzed using light and electron microscopy, cytotoxicity testing, x-ray microanalysis, particle counting, and inductively coupled plasma optical emission spectrometry. Results The filament, a nickel-chromium wire, was coupled to a thicker copper wire coated with silver. The silver coating was sometimes missing. Four tin solder joints attached the wires to each other and coupled the copper/silver wire to the air tube and mouthpiece. All cartomizers had evidence of use before packaging (burn spots on the fibers and electrophoretic movement of fluid in the fibers). Fibers in two cartomizers had green deposits that contained copper. Centrifugation of the fibers produced large pellets containing tin. Tin particles and tin whiskers were identified in cartridge fluid and outer fibers. Cartomizer fluid with tin particles was cytotoxic in assays using human pulmonary fibroblasts. The aerosol contained particles >1 µm comprised of tin, silver, iron, nickel, aluminum, and silicate and nanoparticles (<100 nm) of tin, chromium and nickel. The concentrations of nine of eleven elements in EC aerosol were higher than or equal to the corresponding concentrations in conventional cigarette smoke. Many of the elements identified in EC aerosol are known to cause respiratory distress and disease. Conclusions The presence of metal and silicate particles in cartomizer aerosol demonstrates the need for improved quality control in EC design and manufacture and studies on how EC aerosol impacts the health of

  8. The chemical imprint of silicate dust on the most metal-poor stars

    SciTech Connect

    Ji, Alexander P.; Frebel, Anna; Bromm, Volker E-mail: afrebel@mit.edu

    2014-02-20

    We investigate the impact of dust-induced gas fragmentation on the formation of the first low-mass, metal-poor stars (<1 M {sub ☉}) in the early universe. Previous work has shown the existence of a critical dust-to-gas ratio, below which dust thermal cooling cannot cause gas fragmentation. Assuming that the first dust is silicon-based, we compute critical dust-to-gas ratios and associated critical silicon abundances ([Si/H]{sub crit}). At the density and temperature associated with protostellar disks, we find that a standard Milky Way grain size distribution gives [Si/H]{sub crit} = –4.5 ± 0.1, while smaller grain sizes created in a supernova reverse shock give [Si/H]{sub crit} = –5.3 ± 0.1. Other environments are not dense enough to be influenced by dust cooling. We test the silicate dust cooling theory by comparing to silicon abundances observed in the most iron-poor stars ([Fe/H] < -4.0). Several stars have silicon abundances low enough to rule out dust-induced gas fragmentation with a standard grain size distribution. Moreover, two of these stars have such low silicon abundances that even dust with a shocked grain size distribution cannot explain their formation. Adding small amounts of carbon dust does not significantly change these conclusions. Additionally, we find that these stars exhibit either high carbon with low silicon abundances or the reverse. A silicate dust scenario thus suggests that the earliest low-mass star formation in the most metal-poor regime may have proceeded through two distinct cooling pathways: fine-structure line cooling and dust cooling. This naturally explains both the carbon-rich and carbon-normal stars at extremely low [Fe/H].

  9. Color-control of the persistent luminescence of cadmium silicate doped with transition metals

    SciTech Connect

    Abreu, Carolina M.; Silva, Ronaldo S.; Valerio, Mário E.G.; Macedo, Zélia S.

    2013-04-15

    The structural and optical characterization of cadmium silicate (CdSiO{sub 3}) doped with transition metals is reported. This crystalline system presents intrinsic luminescence and is usually studied as host matrix for rare earth ions. In this work, CdSiO{sub 3} was doped with Mn, Ni and Cr to produce multicolored luminescent materials. Single crystalline CdSiO{sub 3} was obtained via solid state synthesis at 1000 °C/8 h. The valence of the dopants inserted in the host matrix was determined via XANES as 3+ for Cr, 2+ for Ni and both 2+ and 3+ for Mn, according to XANES studies. The optical absorption spectra of the samples presented wide bands in the visible region that were associated with the internal transitions of the dopants. All the samples presented photoluminescent bands near 420 nm, 496 nm and 591 nm, with different relative intensities that yield characteristic luminescence colors ranging from blue to red. - Graphical abstract: Phosphorescence of cadmium silicate doped with transition metals: nature of defects and possible luminescent channels. Highlights: ► CdSiO{sub 3} was doped with Mn, Ni and Cr to produce multicolored phosphors. ► Valence of the dopants was determined as 3+ for Cr, 2+ for Ni and 2+ and 3+ for Mn. ► The presence of absorption bands in the visible region led to self-absorption. ► Self-absorption in some cases can decrease the light output. ► Luminescent channels were created and related to internal transitions of the dopants.

  10. Ca(2+) function in photosynthetic oxygen evolution studied by alkali metal cations substitution.

    PubMed

    Ono, T; Rompel, A; Mino, H; Chiba, N

    2001-10-01

    Effects of adding monovalent alkali metal cations to Ca(2+)-depleted photosystem (PS)II membranes on the biochemical and spectroscopic properties of the oxygen-evolving complex were studied. The Ca(2+)-dependent oxygen evolution was competitively inhibited by K(+), Rb(+), and Cs(+), the ionic radii of which are larger than the radius of Ca(2+) but not inhibited significantly by Li(+) and Na(+), the ionic radii of which are smaller than that of Ca(2+). Ca(2+)-depleted membranes without metal cation supplementation showed normal S(2) multiline electron paramagnetic resonance (EPR) signal and an S(2)Q(A)(-) thermoluminescence (TL) band with a normal peak temperature after illumination under conditions for single turnover of PSII. Membranes supplemented with Li(+) or Na(+) showed properties similar to those of the Ca(2+)-depleted membranes, except for a small difference in the TL peak temperatures. The peak temperature of the TL band of membranes supplemented with K(+), Rb(+), or Cs(+) was elevated to approximately 38 degrees C which coincided with that of Y(D)(+)Q(A)(-) TL band, and no S(2) EPR signals were detected. The K(+)-induced high-temperature TL band and the S(2)Q(A)(-) TL band were interconvertible by the addition of K(+) or Ca(2+) in the dark. Both the Ca(2+)-depleted and the K(+)-substituted membranes showed the narrow EPR signal corresponding to the S(2)Y(Z)(+) state at g = 2 by illuminating the membranes under multiple turnover conditions. These results indicate that the ionic radii of the cations occupying Ca(2+)-binding site crucially affect the properties of the manganese cluster. PMID:11566758

  11. Design and Test of Advanced Thermal Simulators for an Alkali Metal-Cooled Reactor Simulator

    NASA Technical Reports Server (NTRS)

    Garber, Anne E.; Dickens, Ricky E.

    2011-01-01

    The Early Flight Fission Test Facility (EFF-TF) at NASA Marshall Space Flight Center (MSFC) has as one of its primary missions the development and testing of fission reactor simulators for space applications. A key component in these simulated reactors is the thermal simulator, designed to closely mimic the form and function of a nuclear fuel pin using electric heating. Continuing effort has been made to design simple, robust, inexpensive thermal simulators that closely match the steady-state and transient performance of a nuclear fuel pin. A series of these simulators have been designed, developed, fabricated and tested individually and in a number of simulated reactor systems at the EFF-TF. The purpose of the thermal simulators developed under the Fission Surface Power (FSP) task is to ensure that non-nuclear testing can be performed at sufficiently high fidelity to allow a cost-effective qualification and acceptance strategy to be used. Prototype thermal simulator design is founded on the baseline Fission Surface Power reactor design. Recent efforts have been focused on the design, fabrication and test of a prototype thermal simulator appropriate for use in the Technology Demonstration Unit (TDU). While designing the thermal simulators described in this paper, effort were made to improve the axial power profile matching of the thermal simulators. Simultaneously, a search was conducted for graphite materials with higher resistivities than had been employed in the past. The combination of these two efforts resulted in the creation of thermal simulators with power capacities of 2300-3300 W per unit. Six of these elements were installed in a simulated core and tested in the alkali metal-cooled Fission Surface Power Primary Test Circuit (FSP-PTC) at a variety of liquid metal flow rates and temperatures. This paper documents the design of the thermal simulators, test program, and test results.

  12. The Effect of Core-Mantle Differentiation on V, Cr, and Mn: Experimental Metal/Silicate Partitioning Results

    NASA Technical Reports Server (NTRS)

    Chabot, N. L.; Agee, C. B.

    2001-01-01

    The abundances of V, Cr, and Mn are similarly depleted in the Earth and Moon. We present metal/silicate partitioning results which examine if the depletions can be explained by a core formation event. Additional information is contained in the original extended abstract.

  13. Lightning strike fusion: extreme reduction and metal-silicate liquid immiscibility.

    PubMed

    Essene, E J; Fisher, D C

    1986-10-10

    A glassy fulgurite, formed recently on a morainal ridge in southeastern Michigan, contains micrometer- to centimeter-sized metallic globules rich in native silicon, which unmixed from a silica-rich liquid. The unusual character of these globules and their potential for elucidating conditions of fulgurite formation prompted further study. Thermodynamic calculations indicate that temperatures in excess of 2000 K and reducing conditions approaching those of the SiO(2)-Si buffer were needed to form the coexisting metallic and silicate liquids. The phases produced are among the most highly reduced naturally occurring materials known. Some occurrences of other highly reduced minerals may also be due to lightning strike reduction. Extreme reduction and volatilization may also occur during high-temperature events such as lightning strikes in presolar nebulae and impacts of extraterrestrial bodies. As a result of scavenging of platinum-group elements by highly reduced metallic liquids, geochemical anomalies associated with the Cretaceous-Tertiary boundary may have a significant terrestrial component even if produced through bolide impact. PMID:17746479

  14. Highly polar bonds and the meaning of covalency and ionicity--structure and bonding of alkali metal hydride oligomers.

    PubMed

    Bickelhaupt, F Matthias; Solà, Miquel; Guerra, Célia Fonseca

    2007-01-01

    The hydrogen-alkali metal bond is simple and archetypal, and thus an ideal model for studying the nature of highly polar element-metal bonds. Thus, we have theoretically explored the alkali metal hydride monomers, HM, and (distorted) cubic tetramers, (HM)4, with M = Li, Na, K, and Rb, using density functional theory (DFT) at the BP86/TZ2P level. Our objective is to determine how the structure and thermochemistry (e.g., H-M bond lengths and strengths, oligomerization energies, etc.) of alkali metal hydrides depend on the metal atom, and to understand the emerging trends in terms of quantitative Kohn-Sham molecular orbital (KS-MO) theory. The H-M bond becomes longer and weaker, both in the monomers and tetramers, if one descends the periodic table from Li to Rb. Quantitative bonding analyses show that this trend is not determined by decreasing electrostatic attraction but, primarily, by the weakening in orbital interactions. The latter become less stabilizing along Li-Rb because the bond overlap between the singly occupied molecular orbitals (SOMOs) of H* and M* radicals decreases as the metal ns atomic orbital (AO) becomes larger and more diffuse. Thus, the H-M bond behaves as a text-book electron-pair bond and, in that respect, it is covalent, despite a high polarity. For the lithium and sodium hydride tetramers, the H4 tetrahedron is larger than and surrounds the M4 cluster (i.e., H-H > M-M). Interestingly, this is no longer the case in the potassium and rubidium hydride tetramers, in which the H4 tetrahedron is smaller than and inside the M4 cluster (i.e., H-H < M-M). PMID:17328442

  15. In situ insights to Se (S) partitioning between silicate and metallic melts at extreme conditions

    NASA Astrophysics Data System (ADS)

    Borchert, M.; Petitgirard, S.; Appel, K.; Watenphul, A.; Morgenroth, W.

    2012-12-01

    The Earth's core mainly consists of a metallic Fe-Ni mixture. However, seismic observations show that the density is about 5-10% lower than expected for an Fe-Ni alloy under similar pressure and temperature conditions (e.g., [1,2]). This discovery initiated numerous studies to identify and quantify light elements in the Earth0s core. Among others, sulphur has been suggested to be a promisingly candidate to alloy with the metallic core because of its depletion in the crust and the mantle relative to other volatile elements by several orders of magnitude (e.g., [3-5]). In the last decades, several experimental studies have aimed to quantify the sulphur content in the Earth's core and to determine its influence on the physical properties (e.g., [6]). However, experimental data on sulphur partitioning between silicate and metallic liquids at pressures and temperatures relevant for core-mantle boundary conditions are missing. This lack is due to pressure and temperature limitations of conventional experimental approaches (up to 25 GPa and 2200 K). New developments, like laser-heated diamond-anvil cells (LDAC), allow studies at core-mantle boundary conditions, but in-situ chemical analysis of sulphur in LDACs is impossible due to the high absorption of S fluorescence in the diamonds. Instead of sulphur, selenium can be used to model sulphur partitioning between silicate and metallic melts at elevated PT conditions. This is based on the fact that sulphur and selenium can be considered as geochemical twins ([7,8]). The main advantage of this approach is the much higher excitation energy of selenium compared to sulphur, which enables in-situ XRF analysis in LDACs. Here, we present preliminary data on Se partitioning between silicate and metallic melt at extreme conditions. The experiments have been performed in double-sided laser-heated LDACs at the high pressure beamlines P02.2 (DESY, Germany) and ID27 (ESRF, France) as described in [9]. Micro-XRF mappings are used to

  16. Experimental and Theoretical Studies of Pressure Broadened Alkali-Metal Atom Resonance Lines

    NASA Technical Reports Server (NTRS)

    Shindo, F.; Zhu, C.; Kirby, K.; Babb, J. F.

    2006-01-01

    We are carrying out a joint theoretical and experimental research program to study the broadening of alkali atom resonance lines due to collisions with helium and molecular hydrogen for applications to spectroscopic studies of brown dwarfs and extrasolar giant planets.

  17. Plasma assisted spectroscopic monitoring of alkali metals in pressurised combustion and gasification

    SciTech Connect

    Haeyrinen, V.T.; Hernberg, R.G.

    1995-07-01

    The paper describes an instrument for on-line concentration measurement of vaporised alkali compounds in pressurised industrial combustion and gasification processes. The measurement is based on Plasma Excited Alkali Resonance Line Spectroscopy (PEARLS) at the elevated pressure (1-3 MPa) of the process. Results are presented from laboratory calibration measurements and test measurements of sodium and potassium vapours resulting from the combustion of coal powder in a pressurised entrained flow reactor.

  18. First-principles molecular dynamics of liquid alkali metals based on the quantal hypernetted chain theory

    NASA Astrophysics Data System (ADS)

    Kambayashi, Shaw; Chihara, Junzo

    1996-06-01

    A first-principles molecular dynamics (MD) scheme is presented on the basis of the density-functional (DF) theory with use of the the quantal hypernetted chain (QHNC) approximation. The DF theory brings about exact expressions for the ion-electron and ion-ion radial distribution functions (RDF) of an electron-ion mixture as a model of a simple liquid metal. These exact expressions prove that an ion-electron mixture can be treated as a one-component liquid interacting only via a pairwise interaction in the evaluation of the ion-ion RDF, and provide a set of integral equations: one is an exact integral equation for the ion-ion RDF and another for an effective ion-ion interaction, which depends on the ion configuration specified by the ion-ion RDF. Hence, after some approximations are introduced, the MD simulation can be performed to get the ion-ion RDF using the ion-ion interaction determined so as to be consistent to the ion-ion RDF: the MD simulation and the procedure to determine the effective interaction from the QHNC equation are performed iteratively. This MD simulation coupled with the QHNC equation (QHNC-MD method) for the effective interaction provides a first-principles calculation of structures of simple liquid metal: the ion-ion and electron-ion RDF's, the charge distributions of an ion and a pseudoatom, the effective ion-ion interaction and the ion-ion bridge function are evaluated in a self-consistent manner from the atomic number as the only input. We have applied this QHNC-MD method to Li, Na, K, Rb, and Cs near the melting temperature using up to 16 000 particles for the MD simulation. It is found that the convergence of the effective ion-ion interaction is fast enough for practical application to alkali metals; two MD runs are enough for convergence within accuracy of 3 to 4 digits, if the initial effective potential is properly set up. The structure factors, thus obtained, show excellent agreement with the experimental data observed by x-ray and

  19. Raman and nuclear magnetic resonance investigation of alkali metal vapor interaction with alkene-based anti-relaxation coating

    NASA Astrophysics Data System (ADS)

    Tretiak, O. Yu.; Blanchard, J. W.; Budker, D.; Olshin, P. K.; Smirnov, S. N.; Balabas, M. V.

    2016-03-01

    The use of anti-relaxation coatings in alkali vapor cells yields substantial performance improvements compared to a bare glass surface by reducing the probability of spin relaxation in wall collisions by several orders of magnitude. Some of the most effective anti-relaxation coating materials are alpha-olefins, which (as in the case of more traditional paraffin coatings) must undergo a curing period after cell manufacturing in order to achieve the desired behavior. Until now, however, it has been unclear what physicochemical processes occur during cell curing, and how they may affect relevant cell properties. We present the results of nondestructive Raman-spectroscopy and magnetic-resonance investigations of the influence of alkali metal vapor (Cs or K) on an alpha-olefin, 1-nonadecene coating the inner surface of a glass cell. It was found that during the curing process, the alkali metal catalyzes migration of the carbon-carbon double bond, yielding a mixture of cis- and trans-2-nonadecene.

  20. Raman and nuclear magnetic resonance investigation of alkali metal vapor interaction with alkene-based anti-relaxation coating.

    PubMed

    Tretiak, O Yu; Blanchard, J W; Budker, D; Olshin, P K; Smirnov, S N; Balabas, M V

    2016-03-01

    The use of anti-relaxation coatings in alkali vapor cells yields substantial performance improvements compared to a bare glass surface by reducing the probability of spin relaxation in wall collisions by several orders of magnitude. Some of the most effective anti-relaxation coating materials are alpha-olefins, which (as in the case of more traditional paraffin coatings) must undergo a curing period after cell manufacturing in order to achieve the desired behavior. Until now, however, it has been unclear what physicochemical processes occur during cell curing, and how they may affect relevant cell properties. We present the results of nondestructive Raman-spectroscopy and magnetic-resonance investigations of the influence of alkali metal vapor (Cs or K) on an alpha-olefin, 1-nonadecene coating the inner surface of a glass cell. It was found that during the curing process, the alkali metal catalyzes migration of the carbon-carbon double bond, yielding a mixture of cis- and trans-2-nonadecene. PMID:26957176

  1. Si isotope fractionation between Si-poor metal and silicate melt at pressure-temperature conditions relevant to metal segregation in small planetary bodies

    NASA Astrophysics Data System (ADS)

    Kempl, J.; Vroon, P. Z.; Zinngrebe, E.; van Westrenen, W.

    2013-04-01

    Experimental investigations of Si isotope fractionation between Si-bearing metal alloy and silicate phases have to date been limited to high pressure (1-7 GPa) and high temperature (1800-2200 °C) conditions at highly reducing conditions, to optimize applicability of results to early core formation processes in the Earth. Here, we assess the extent and mechanism of Si isotopic fractionation at conditions relevant to metal segregation in small (km-scale) planetary bodies, using samples obtained from an industrial-scale blast furnace of Tata Steel (IJmuiden, the Netherlands). During the low-pressure, high-temperature process of steelmaking inhomogeneous blast furnace burden consisting of pre- and untreated iron ore, iron silicates and coke is reduced to oxygen fugacities near the C-CO buffer, resulting in the segregation of a metal phase containing only ∼0.3 wt% Si. Seven sample sets, each comprising a metal alloy and a silicate slag, were taken during tapping of the blast furnace at tapping temperatures between 1400 °C and 1600 °C. We find large isotopic mass fractionation between metal and silicate, with Δ30Sisilicate-metal varying between 0.7‰ and 1.6‰, values that are as high as previously obtained in high-pressure, highly reduced experiments. A model for metal-silicate Si isotope fractionation in blast furnaces can explain both the sense and magnitude of fractionation, if the presence of SiO-bearing vapour is explicitly taken into account. Our data indicate that significant Si isotope fractionation can occur between metal and silicate at low-pressure, high-temperature and only mildly reducing conditions for which Si solubility in molten Fe-rich metal is low. This suggests an important role for SiO at low confining pressures. Our data can be applied to models of aubrite meteorite formation through high-temperature differentiation of an enstatite chondrite parent body. Our calculations suggest a far larger degree of rehomogenisation during differentiation

  2. Synthesis and Properties of Alkali Metal Intercalated Fullerene-like MS2 (M=W,Mo) Nanoparticles

    NASA Astrophysics Data System (ADS)

    Zak, Alla; Feldman, Yishay; Lyakhovitskaya, Vera; Leitus, Gregory; Popovitz-Biro, Ronit; Wachtel, Ellen; Cohen, Hagai; Reich, Shimon; Tenne, Reshef

    2002-10-01

    Layered metal disulfides - MoS2 and WS2 in the form of fullerene-like (IF) nanoparticles and in the form of platelets (crystallites of the 2H polytype) have been intercalated by exposure to alkali metal (potassium and sodium) vapor using a two-zone transport method. The composition of the intercalated systems was established using X-ray energy dispersive spectrometer (EDS) and X-ray photoelectron spectroscopy (XPS). X-ray powder diffraction (XRD) analysis and transmission electron microscopy (TEM) of the samples, which were not exposed to the ambient atmosphere, showed that they suffered little change in their lattice parameters. On the other hand, after exposure to ambient atmosphere, substantial increase in the interplanar spacing (3-5 Å) was observed for the intercalated phases. Insertion of one to two water molecules per intercalated metal atom was suggested as a possible explanation for this large expansion along the c-axis. The modifications in magnetic and transport properties of the intercalated materials were investigated, and are believed to occur via charge transfer from the alkali metal to the conduction band of the host lattice. Restacking of the MS2 layers after prolonged exposure to the atmosphere and recovery of the pristine compound properties were observed as a result of deintercalation of the metal atoms.

  3. Alkali metals in circulating fluidized bed combustion of biomass and coal: measurements and chemical equilibrium analysis

    SciTech Connect

    Michal P. Glazer; Nafees A. Khan; Wiebren de Jong; Hartmut Spliethoff; Heiko Schuermann; Penelope Monkhouse

    2005-10-01

    Combustion and co-combustion experiments with four kinds of straw, specially selected for their different alkali, Cl, and Si contents, and Colombian black coal were carried out in a circulating fluidized bed (CFB) reactor at Delft University of Technology. The influence of operating conditions and fuel composition on the release of the alkali compounds to the gas phase was investigated. The amount of the total gas-phase sodium and potassium compounds in the flue gases was measured with excimer laser induced fluorescence (ELIF). The results show that the release of gaseous alkali species depends on fuel composition, in particular the K/Cl and K/Si ratios in the fuel. The fuels with high K and Cl values show higher concentrations of the gaseous alkalis. A synergetic effect of the co-combustion with coal was observed, which led to a strong decrease in gaseous alkali concentrations. Together with experiments, chemical equilibrium modeling was performed to help in interpreting the experimental data. The calculations confirmed that the equilibrium is very strongly influenced by the composition of the fuel blend. Moreover, the simulations provided more information on sequestering of alkali species. 22 refs., 5 figs., 4 tabs.

  4. Experimental Constraints on the Solubility and Partitioning of Carbon between Metallic and Silicate Melt in a Shallow Magma Ocean

    NASA Astrophysics Data System (ADS)

    Chi, Han

    The budget and origin of carbon in Earth and other terrestrial planets are debated and one of the key unknowns is the behavior and fate of carbon during early planetary processes including accretion, core formation, and magma ocean crystallization. Here we determine, experimentally, the solubility of carbon in coexisting Fe-Ni alloy melt and basaltic silicate melt in shallow magma ocean conditions, i.e., at 1-3 GPa, 1500-1800 °C. Oxygen fugacity of the experiments, estimated based on Fe (in metallic alloy melt)-FeO (in silicate melt) equilibrium, varied from IW-0.37 and IW-1.02, where IW refers to the oxygen fugacity imposed by the coexistence of iron and wustite. Four different starting mixes, each with 7:3 silicate:metal mass ratio, with silicate melt NBO/T (estimated proportion of non-bridging oxygen with respect to tetrahedral cations) ranging from 0.81 to 1.54 were studied. Concentrations of carbon in the alloy melt were determined using electron microprobe whereas carbon contents of quenched basaltic glasses were determined using secondary ionization mass spectrometry (SIMS). Identification of carbon and hydrogen-bearing species in silicate glasses was performed using Raman spectroscopy. Our results show that carbon in the metallic melt varies between 4.39 and 7.43 wt.% and increases with increasing temperature and modestly with increasing pressure. Carbon concentration in the silicate melts, on the other hand, varies from 11+/-1 ppm to 111+/-7 ppm and is negatively correlated with pressure but positively correlated with temperature, the NBO/T (non-bridging per tetrahydron, an index of the depolymerization of the silicate melt), the oxygen fugacity and the water content of the silicate melts. Raman and FT-IR results show that at our experimental conditions, carbon in silicate melt is dissolved as hydrogenated species, in addition to . The calculated carbon partition coefficient varies from 510+/-53 to 5369+/-217 and varies systematically as a function of P

  5. Silicate-Metal Partitioning of Trace Elements: An Exploratory Ab Initio Molecular Dynamics Study

    NASA Astrophysics Data System (ADS)

    Künzel, D.; Jahn, S.

    2014-12-01

    Partition coefficients of trace elements are very important for the reconstruction of Earth formation and evolution processes. As such processes typically take place at extreme conditions of pressure and temperature, it is still challenging to obtain experimental data. However, recent developments in super-computing facilities and in computational methods have made it possible to obtain supplementing information on melts and element partitioning from ab initio atomistic calculations. The model system used in this pilot study consists of two different melts: a simple Fe-Ni alloy representing the metal and a silicate phase with a varying ratio of Fe and Mg ((Fe,Mg)2SiO4). Traces of Ni or Cr are added to each system. Molecular dynamics simulations based on density functional theory are initially run at 2500 K and ambient pressure, using the CPMD and CP2K software packages. Conditions are chosen so that the results can be compared to available experimental data in order to assess the feasibility of the approach and the quality of its results. However, preliminary results at increased pressure and temperature conditions that are more relevant for core formation will be presented as well. The results of the calculations include information on the melt structure, such as coordination environment, nearest neighbor distance and x-ray diffraction structure factors. The calculations at ambient pressure show that the behavior of Ni atoms in the silicate melt shows similarities to Mg and differs clearly from Fe. First results with a Cr trace show that it resembles Fe rather than Ni. Furthermore, thermodynamic integration is able to provide thermodynamic information about the exchange of trace elements between both phases. It is possible to obtain the energy difference connected to this exchange, which can then be used to estimate partition factors. First results on the Ni partitioning will be presented.

  6. Study on the Characteristics of an Alkali-Metal Thermoelectric Power Generation System

    NASA Astrophysics Data System (ADS)

    Lee, Wook-Hyun; Hwang, Hyun-Chang; Lee, Ji-Su; Kim, Pan-Jo; Lim, Sang-Hyuk; Rhi, Seok-Ho; Lee, Kye-Bock; Lee, Ki-Woo

    2015-10-01

    In the present study, a numerical simulation and experimental studies of an alkali-metal thermoelectric energy converter (AMTEC) system were carried out. The present, unique AMTEC model consists of an evaporator, a β-alumina solid electrolyte (BASE) tube, a condenser, and an artery cable wick. The key points for operation of the present AMTEC were 1100 K in the evaporator and 600 K in the condenser. A numerical model based on sodium-saturated porous wicks was developed and shown to be able to simulate the AMTEC system. The simulation results show that the AMTEC system can generate up to 100 W with a given design. The AMTEC system developed in the present work and used in the practical investigations could generate an electromotive force of 7 V. Artery wick and evaporator wick structures were simulated for the optimum design. Both sodium-saturated wicks were affected by numerous variables, such as the input heat power, cooling temperature, sodium mass flow rate, and capillary-driven fluid flow. Based on an effective thermal conductivity model, the presented simulation could successfully predict the system performance. Based on the numerical simulation, the AMTEC system operates with efficiency near 10% to 15%. In the case of an improved BASE design, the system could reach efficiency of over 30%. The system was designed for 0.6 V power, 25 A current, and 100 W power input. In addition, in this study, the temperature effects in each part of the AMTEC system were analyzed using a heat transfer model in porous media to apply to the computational fluid dynamics at a predetermined temperature condition for the design of a 100-W AMTEC prototype. It was found that a current density of 0.5 A/cm2 to 0.9 A/cm2 for the BASE is suitable when the temperatures of the evaporator section and condenser section are 1100 K and 600 K, respectively.

  7. Synthesis and structural determination of alkali and alkaline earth metal containing bismuth vanadates

    NASA Astrophysics Data System (ADS)

    Bliesner, Rebecca Jean

    Exploratory synthesis plays an important role in the quest to discover new materials. There are very few structurally characterized alkali metal containing bismuth vanadates. Hybridization of the 6s and 6p orbitals of Bi 3+ and the resulting lone electron pair yields some very interesting stereochemistry and steric related properties. Some of those properties include ferroelectricity, ferroelasticity, electronic and ionic conduction, superconductivity, nonlinear optical capabilities and selective catalysis. Systematic exploration of the Na-Bi-V ternary system produced a new phase of NaBi3V2O10. This material crystallizes in the P1¯ space group and the reported oxygen ion conductivity is apparently due to the presence of interstitial oxygen rather than oxygen vacancies. Stabilization of the tetragonal scheelite phase of BiVO4 has been achieved by the substitution of a M2+ for Bi3+ . This has not been accomplished previously by a M2+ cation substitution. The compound Ca0.29Bi0.71VO 3.855 crystallizes in the P4¯ space group. An investigation of the K-Bi-V ternary system resulted in the discovery of a new potassium vanadate. K10Bi4V4O 21 crystallizes in the P6¯ space group with a equal to 10.205(2)A and c equal to 7.669(2)A. Other new compounds prepared, for which structures have not been determined are alpha-Na3BiV2O8, beta-Na3BiV 2O8, K8Bi5V5O24, Rb2BiVO5, a rubidium compound with a 3:3:2 stoichiometric ratio of Rb:Bi:V, a rubidium compound with 2:1:1, a sodium compound with 2:1:1 and a lithium compound with a 1:1:1 stoichiometric ratio of Li:Bi:V.

  8. N-alkyl pyrrolidone ether podands as versatile alkali metal ion chelants.

    PubMed

    Perrin, Andrea; Myers, Dominic; Fucke, Katharina; Musa, Osama M; Steed, Jonathan W

    2014-02-28

    This work explores the coordination chemistry of a bis(pyrrolidone) ether ligand. Pyrrolidones are commercially important functional groups because of the high polarity and hence high hydrophilicity and surface affinity. An array of alkali metal ion complexes of a podand bearing two pendant pyrrolidone functionalities, namely 1-{2-[2-(2-oxo-pyrrolid-1-yl)-ethoxy]-ethyl}-pyrrolid-2-one (1) are reported. Reaction of this ligand with sodium hexafluorophosphate gives two discrete species of formulae [Na(1)2]PF6 (3) and [Na3(H2O)2(μ-1)2](PF6)3 (4), and a coordination polymer {[Na3(μ3-1)3(μ2-1)](PF6)3}n (5). The same reaction in methanol gives a 1 : 1 complex, namely [Na2(μ-1)2(MeOH)2](PF6)2 (6). Use of tetraphenyl borate as a less coordinating counter ion gives [Na2(1)2(H2O)4](BPh4)2 (7) and [Na2(1)4](BPh4)2 (8). Two potassium complexes have also been isolated, a monomer [K(1)2]PF6 (9) and a cyclic tetramer [K4(μ4-H2O)2(μ-1)4](PF6)4 (10). The structures illustrate the highly polar nature of the amide carbonyl moiety within bis(pyrrolidone) ethers with longer interactions to the ether oxygen atom. The zinc complex is also reported and {[ZnCl2(μ-1)]}n (11) exhibits bonding only to the carbonyl moieties. The ether oxygen atom is not necessary for Na(+) complexation as exemplified by the structure of the sodium complex of the analogue 1,3-bis(pyrrolid-2-on-1-yl)butane (2). Reaction of compound 1 with lithium salts results in isolation of the protonated ligand. PMID:24336897

  9. Valence and metal/silicate partitioning of Mo: Implications for conditions of Earth accretion and core formation

    NASA Astrophysics Data System (ADS)

    Righter, K.; Danielson, L. R.; Pando, K. M.; Shofner, G. A.; Sutton, S. R.; Newville, M.; Lee, C.-T.

    2016-03-01

    To better understand and predict the partition coefficient of Mo at the conditions of the deep interior of Earth and other terrestrial planets or bodies, we have undertaken new measurements of the valence and partitioning of Mo. X-ray absorption near edge structure (XANES) K-edge spectra for Mo have been measured in a series of Fe-bearing glasses produced at 1 bar and higher PT conditions. High pressure experiments have been carried out up to 19 GPa in order to better understand the effect of pressure on Mo partitioning. And, finally, a series of experiments at very low fO2 conditions and high Si content metallic liquids has been carried out to constrain the effect of Si on the partitioning of Mo between metallic liquids and silicate melt. The valence measurements demonstrate that Mo undergoes a transition from 4+ to 6+ near IW-1, in general agreement with previous 1 bar studies on FeO-free silicate melts. High pressure experiments demonstrate a modest pressure dependence of D (Mo) metal/silicate and, combined with previous results, show a significant decrease with pressure that must be quantified in any predictive expression. Finally, the effect of dissolved Si in Fe-rich metallic liquid is to decrease D (Mo) significantly, as suggested by previous work in metallurgical systems. The effect of pressure, temperature, oxygen fugacity, metallic liquid composition, and silicate melt composition can be quantified by using multiple linear regression of available experimental data for Mo. Our XANES results show that Mo will be 4+ at conditions of core formation, so only experiments carried out at fO2 of IW-1 and lower were used in the regressions. Application of predictive expressions to Earth accretion shows that D (Mo) decreases to values consistent with an equilibrium scenario for early Earth core-mantle. The Mo content of the primitive upper mantle (PUM) can be attained by metal-silicate equilibrium involving S-, C-, and Si-bearing metallic liquid, and peridotite

  10. Metal-Silicate Partitioning of Various Siderophile Elements at High Pressure and High Temperatures: a Diamond Anvil Cell Study

    NASA Astrophysics Data System (ADS)

    Badro, J.; Blanchard, I.; Siebert, J.

    2015-12-01

    Core formation is the major chemical fractionation that occurred on Earth. This event is widely believed to have happened at pressures of at least 40 GPa and temperatures exceeding 3000 K. It has left a significant imprint on the chemistry of the mantle by removing most of the siderophile (iron-loving) elements from it. Abundances of most siderophile elements in the bulk silicate Earth are significantly different than those predicted from experiments at low P-T. Among them, vanadium, chromium, cobalt and gallium are four siderophile elements which abundances in the mantle have been marked by core formation processes. Thus, understand their respective abundance in the mantle can help bringing constraints on the conditions of Earth's differentiation. We performed high-pressure high-temperature experiments using laser heating diamond anvil cell to investigate the metal-silicate partitioning of those four elements. Homogeneous glasses doped in vanadium, chromium, cobalt and gallium were synthesized using a levitation furnace and load inside the diamond anvil cell along with metallic powder. Samples were recovered using a Focused Ion Beam and chemically analyzed using an electron microprobe. We investigate the effect of pressure, temperature and metal composition on the metal-silicate partitioning of V, Cr, Co and Ga. Three previous studies focused on V, Cr and Co partitioning at those conditions of pressure and temperature, but none explore gallium partitioning at the relevant extreme conditions of core formation. We will present the first measurements of gallium metal-silicate partitioning performed at the appropriate conditions of pressure and temperature of Earth's differentiation.

  11. Metal/sulfide-silicate intergrowth textures in EL3 meteorites: Origin by impact melting on the EL parent body

    NASA Astrophysics Data System (ADS)

    van Niekerk, Deon; Keil, Klaus

    2011-10-01

    We document the petrographic setting and textures of Fe,Ni metal, the mineralogy of metallic assemblages, and the modal mineral abundances in the EL3 meteorites Asuka (A-) 881314, A-882067, Allan Hills 85119, Elephant Moraine (EET) 90299/EET 90992, LaPaz Icefield 03930, MacAlpine Hills (MAC) 02635, MAC 02837/MAC 02839, MAC 88136, Northwest Africa (NWA) 3132, Pecora Escarpment 91020, Queen Alexandra Range (QUE) 93351/QUE 94321, QUE 94594, and higher petrologic type ELs Dar al Gani 1031 (EL4), Sayh al Uhaymir 188 (EL4), MAC 02747 (EL4), QUE 94368 (EL4), and NWA 1222 (EL5). Large metal assemblages (often containing schreibersite and graphite) only occur outside chondrules and are usually intergrown with silicate minerals (euhedral to subhedral enstatite, silica, and feldspar). Sulfides (troilite, daubréelite, and keilite) are also sometimes intergrown with silicates. Numerous authors have shown that metal in enstatite chondrites that are interpreted to have been impact melted contains euhedral crystals of enstatite. We argue that the metal/sulfide-silicate intergrowths in the ELs we studied were also formed during impact melting and that metal in EL3s thus does not retain primitive (i.e., nebular) textures. Likewise, the EL4s are also impact-melt breccias. Modal abundances of metal in the EL3s and EL4s range from approximately 7 to 30 wt%. These abundances overlap or exceed those of EL6s, and this is consistent either with pre-existing heterogeneity in the parent body or with redistribution of metal during impact processes.

  12. Alkali-Metal-Ion-Functionalized Graphene Oxide as a Superior Anode Material for Sodium-Ion Batteries.

    PubMed

    Wan, Fang; Li, Yu-Han; Liu, Dai-Huo; Guo, Jin-Zhi; Sun, Hai-Zhu; Zhang, Jing-Ping; Wu, Xing-Long

    2016-06-01

    Although graphene oxide (GO) has large interlayer spacing, it is still inappropriate to use it as an anode for sodium-ion batteries (SIBs) because of the existence of H-bonding between the layers and ultralow electrical conductivity which impedes the Na(+) and e(-) transformation. To solve these issues, chemical, thermal, and electrochemical procedures are traditionally employed to reduce GO nanosheets. However, these strategies are still unscalable, consume high amounts of energy, and are expensive for practical application. Here, for the first time, we describe the superior Na storage of unreduced GO by a simple and scalable alkali-metal-ion (Li(+) , Na(+) , K(+) )-functionalized process. The various alkali metals ions, connecting with the oxygen on GO, have played different effects on morphology, porosity, degree of disorder, and electrical conductivity, which are crucial for Na-storage capabilities. Electrochemical tests demonstrated that sodium-ion-functionalized GO (GNa) has shown outstanding Na-storage performance in terms of excellent rate capability and long-term cycle life (110 mAh g(-1) after 600 cycles at 1 A g(-1) ) owing to its high BET area, appropriate mesopore, high degree of disorder, and improved electrical conductivity. Theoretical calculations were performed using the generalized gradient approximation (GGA) to further study the Na-storage capabilities of functionalized GO. These calculations have indicated that the Na-O bond has the lowest binding energy, which is beneficial to insertion/extraction of the sodium ion, hence the GNa has shown the best Na-storage properties among all comparatives functionalized by other alkali metal ions. PMID:27136376

  13. Model analysis of ground-state dissociation energies and equilibrium separations in alkali-metal diatomic compounds

    NASA Astrophysics Data System (ADS)

    Lombardi, Erminio; Jansen, Laurens

    1986-05-01

    Ground-state dissociation energies De and equilibrium distances Re for the series of homonuclear alkali-metal diatomic molecules Li2,Na2,..., as well as those for six heteronuclear alkali-metal diatomic compounds, are evaluated on the basis of a simple valence-bond model. Each alkali-metal atom in a diatomic molecule is characterized by two quantities: a Gaussian parameter βe of the valence-electron function and a valence-to-core ``relative-size'' parameter γ≡(βc/βe)2, with βc the Gaussian parameter for the core-electron charge distribution. For the homonuclear diatomic molecules, accurate results are obtained with a 2s Gaussian valence function (r2-a2)G orthogonalized to the core. For each homonuclear diatomic molecule there exists an optimal (βe,γ) set yielding values of De and Re in practically quantitative agreement with experiment. The quantities βe and γ exhibit the expected physical behavior over the series in that βe decreases from Li2 to Cs2, and γ is highest for the lightest diatomic molecule Li2. The compounds K2, Rb2, and Cs2 are found to be ``Heitler-London'' molecules to within 5% of their binding energies. An approximate, similar, analysis of six heteronuclear diatomic compounds yields close agreement with experiment for LiNa and RbCs, whereas with the other four compounds (LiK, NaK, NaRb, and NaCs) the agreement with experimental De and Re is to within at most 5%. Also RbCs is a ``Heitler-London'' molecule to a very good approximation.

  14. Formation and Reduction of Pollutants in CFBC: From Heavy Metals, Particulates, Alkali, NOx, N2O, SOx, HCl

    NASA Astrophysics Data System (ADS)

    Winter, Franz

    Due to the advantages of fluidized bed combustors a wide range of different fuels is utilized. The fuels range from anthracite, medium and low rank coals to peat, wood residues, biomass waste, sewage sludge and other sludges to plastics and municipal solid waste. Because of this wide range of fuels pollutants such as heavy metals, particulates, alkali, NO, NO2, N2O, SO2, SO3 and HCI may be formed during the fuel conversion process depending on the fuel and operating conditions.

  15. Structure of the alkali-metal-atom + strontium molecular ions: Towards photoassociation and formation of cold molecular ions

    SciTech Connect

    Aymar, M.; Dulieu, O.; Guerout, R.

    2011-08-14

    The potential energy curves, permanent and transition dipole moments, and the static dipolar polarizability, of molecular ions composed of one alkali-metal atom and a strontium ion are determined with a quantum chemistry approach. The molecular ions are treated as effective two-electron systems and are treated using effective core potentials including core polarization, large gaussian basis sets, and full configuration interaction. In the perspective of upcoming experiments aiming at merging cold atom and cold ion traps, possible paths for radiative charge exchange, photoassociation of a cold lithium or rubidium atom and a strontium ion are discussed, as well as the formation of stable molecular ions.

  16. Collimated, single-pass atom source from a pulsed alkali metal dispenser for laser-cooling experiments

    SciTech Connect

    Moore, Kevin L.; Purdy, Thomas P.; Murch, Kater W.; Leslie, Sabrina; Gupta, Subhadeep; Stamper-Kurn, Dan M.

    2005-02-01

    We have developed an improved scheme for loading atoms into a magneto-optical trap (MOT) from a directed rubidium alkali metal dispenser in <10{sup -10} Torr ultrahigh vacuum conditions. A current-driven dispenser was surrounded with a cold absorbing 'shroud' held at {<=}0 deg. C, pumping rubidium atoms not directed into the MOT. This nearly eliminates background atoms and reduces the detrimental rise in pressure normally associated with these devices. The system can be well-described as a current-controlled, rapidly switched, two-temperature thermal beam, and was used to load a MOT with 3x10{sup 8} atoms.

  17. Sensitive determination of the spin polarization of optically pumped alkali-metal atoms using near-resonant light.

    PubMed

    Ding, Zhichao; Long, Xingwu; Yuan, Jie; Fan, Zhenfang; Luo, Hui

    2016-01-01

    A new method to measure the spin polarization of optically pumped alkali-metal atoms is demonstrated. Unlike the conventional method using far-detuned probe light, the near-resonant light with two specific frequencies was chosen. Because the Faraday rotation angle of this approach can be two orders of magnitude greater than that with the conventional method, this approach is more sensitive to the spin polarization. Based on the results of the experimental scheme, the spin polarization measurements are found to be in good agreement with the theoretical predictions, thereby demonstrating the feasibility of this approach. PMID:27595707

  18. Sensitive determination of the spin polarization of optically pumped alkali-metal atoms using near-resonant light

    PubMed Central

    Ding, Zhichao; Long, Xingwu; Yuan, Jie; Fan, Zhenfang; Luo, Hui

    2016-01-01

    A new method to measure the spin polarization of optically pumped alkali-metal atoms is demonstrated. Unlike the conventional method using far-detuned probe light, the near-resonant light with two specific frequencies was chosen. Because the Faraday rotation angle of this approach can be two orders of magnitude greater than that with the conventional method, this approach is more sensitive to the spin polarization. Based on the results of the experimental scheme, the spin polarization measurements are found to be in good agreement with the theoretical predictions, thereby demonstrating the feasibility of this approach. PMID:27595707

  19. Measuring the spin polarization of alkali-metal atoms using nuclear magnetic resonance frequency shifts of noble gases

    NASA Astrophysics Data System (ADS)

    Liu, X. H.; Luo, H.; Qu, T. L.; Yang, K. Y.; Ding, Z. C.

    2015-10-01

    We report a novel method of measuring the spin polarization of alkali-metal atoms by detecting the NMR frequency shifts of noble gases. We calculated the profile of 87Rb D1 line absorption cross sections. We then measured the absorption profile of the sample cell, from which we calculated the 87Rb number densities at different temperatures. Then we measured the frequency shifts resulted from the spin polarization of the 87Rb atoms and calculated its polarization degrees at different temperatures. The behavior of frequency shifts versus temperature in experiment was consistent with theoretical calculation, which may be used as compensative signal for the NMRG closed-loop control system.

  20. Alkali Metal Ion Complexes with Phosphates, Nucleotides, Amino Acids, and Related Ligands of Biological Relevance. Their Properties in Solution.

    PubMed

    Crea, Francesco; De Stefano, Concetta; Foti, Claudia; Lando, Gabriele; Milea, Demetrio; Sammartano, Silvio

    2016-01-01

    Alkali metal ions play very important roles in all biological systems, some of them are essential for life. Their concentration depends on several physiological factors and is very variable. For example, sodium concentrations in human fluids vary from quite low (e.g., 8.2 mmol dm(-3) in mature maternal milk) to high values (0.14 mol dm(-3) in blood plasma). While many data on the concentration of Na(+) and K(+) in various fluids are available, the information on other alkali metal cations is scarce. Since many vital functions depend on the network of interactions occurring in various biofluids, this chapter reviews their complex formation with phosphates, nucleotides, amino acids, and related ligands of biological relevance. Literature data on this topic are quite rare if compared to other cations. Generally, the stability of alkali metal ion complexes of organic and inorganic ligands is rather low (usually log K < 2) and depends on the charge of the ligand, owing to the ionic nature of the interactions. At the same time, the size of the cation is an important factor that influences the stability: very often, but not always (e.g., for sulfate), it follows the trend Li(+) > Na(+) > K(+) > Rb(+) > Cs(+). For example, for citrate it is: log K ML = 0.88, 0.80, 0.48, 0.38, and 0.13 at 25 °C and infinite dilution. Some considerations are made on the main aspects related to the difficulties in the determination of weak complexes. The importance of the alkali metal ion complexes was also studied in the light of modelling natural fluids and in the use of these cations as probes for different processes. Some empirical relationships are proposed for the dependence of the stability constants of Na(+) complexes on the ligand charge, as well as for correlations among log K values of NaL, KL or LiL species (L = generic ligand). PMID:26860301

  1. Third order nonlinear optical properties and optical limiting behavior of alkali metal complexes of p-nitrophenol

    NASA Astrophysics Data System (ADS)

    Thangaraj, M.; Vinitha, G.; Sabari Girisun, T. C.; Anandan, P.; Ravi, G.

    2015-10-01

    Optical nonlinearity of metal complexes of p-nitrophenolate (M=Li, Na and K) in ethanol is studied by using a continuous wave (cw) diode pumped Nd:YAG laser (532 nm, 50 mW). The predominant mechanism of observed nonlinearity is thermal in origin. The nonlinear refractive index and the nonlinear absorption coefficient of the samples were found to be in the order of 10-8 cm2/W and 10-3 cm/W respectively. Magnitude of third-order optical parameters varies according to the choice of alkali metal chosen for metal complex formation of p-nitrophenolate. The third-order nonlinear susceptibility was found to be in the order of 10-6 esu. The observed saturable absorption and the self-defocusing effect were used to demonstrate the optical limiting action at 532 nm by using the same cw laser beam.

  2. Alkali metal salts of rutin - Synthesis, spectroscopic (FT-IR, FT-Raman, UV-VIS), antioxidant and antimicrobial studies.

    PubMed

    Samsonowicz, M; Kamińska, I; Kalinowska, M; Lewandowski, W

    2015-12-01

    In this work several metal salts of rutin with lithium, sodium, potassium, rubidium and cesium were synthesized. Their molecular structures were discussed on the basis of spectroscopic (FT-IR, FT-Raman, UV-VIS) studies. Optimized geometrical structure of rutin was calculated by B3LYP/6-311++G(∗∗) method and sodium salt of rutin were calculated by B3LYP/LanL2DZ method. Metal chelation change the biological properties of ligand therefore the antioxidant (FRAP and DPPH) and antimicrobial activities (toward Escherichia coli, Staphylococcus aureus, Enterococcus faecium, Proteus vulgaris, Pseudomonas aeruginosa, Klebsiella pneumonia, Candida albicans and Saccharomyces cerevisiae) of alkali metal salts were evaluated and compared with the biological properties of rutin. PMID:26184478

  3. Transition rates for lithium-like ions, sodium-like ions, and neutral alkali-metal atoms

    SciTech Connect

    Johnson, W.R.; Liu, Z.W.; Sapirstein, J.

    1996-11-01

    Third-order many-body perturbation theory is used to obtain E1 transition amplitudes for ions of the lithium and sodium isoelectronic sequences and for the neutral alkali-metal atoms potassium, rubidium, cesium, and francium. Complete angular reductions of the first, second, and third-order amplitudes are given. Tables of transition energies and rates are given for the 2p{sub {1/2}} {yields} 2s{sub {1/2}}, 2p{sub 3/2} {yields} 2s{sub {1/2}}, 3s{sub {1/2}} {yields} 2p{sub {1/2}}, and 3s{sub {1/2}} {yields} 2p{sub 3/2} transitions in the lithium isoelectronic sequence and for the corresponding 3p{sub 1/2} {yields} 3s{sub 1/2}, 3p{sub 3/2} {yields} 3s{sub {1/2}}, 4s{sub {1/2}} {yields} 3p{sub 1/2}, and 4s{sub {1/2}} {yields} 3p{sub 3/2} transitions in the sodium sequence. For neutral alkali atoms, amplitudes of np{sub {1/2}} {yields} ns{sub {1/2}}, np{sub 3/2} {yields} ns{sub {1/2}}, (n + 1)s{sub {1/2}} {yields} np{sub {1/2}}, and (n + 1)s{sub {1/2}} {yields} np{sub 3/2} transitions are evaluated, where n is the principal quantum number of the valence electron in the atomic ground state, Semi-empirical corrections for the omitted fourth- and higher-order terms in perturbation theory are given for the neutral alkali-metal atoms. Comparisons with previous high-precision calculations and with experiment are made. 42 refs., 1 fig., 12 tabs.

  4. The Effect of Pressure on Siderophile-Element (Ni, Co, Mo, W, and P) Metal-Silicate Partition Coefficients

    NASA Astrophysics Data System (ADS)

    Righter, K.; Drake, M. J.

    1995-09-01

    Quantification of the effect of pressure on siderophile element metal-silicate partition coefficients (D) is essential in modelling the accretion histories of the the Earth and terrestrial planets [1], as metal-silicate equilibria may have been set over a range of pressures [2]. We report siderophile element partition coefficients from metal-silicate equilibrium experiments done at 10 and 15 kb, and 1300 degrees C. These new results show that metal-silicate partition coefficients for Ni (Fig. 1), Co, and P decrease with increasing pressure (at constant T and relative fO(sub)2), while those for Mo and W increase. Experiments were done in a 1/2" piston cylinder apparatus, with T, P and fO(sub)2 controlled and monitored as described in a previous study [3]. Synthetic basalt [see 3] powder, doped with 5 wt% levels of either MoO3, WO3 or apatite, was loaded into Fe54Ni29Co17 or Fe64Ni36 tubing, which was closed either by welding or plugging the open ends with small, tapered caps of the same alloy composition. The samples were quenched after 4 to 6 hrs. The metal and glass in the run products are then analyzed by electron microprobe to obtain a solid metal/liquid silicate (SM/LS) partition coefficient for a given element (D = wt% element in metal/ wt% element in glass). For several experiments, NiS was added as a sulfur source, and thus stabilizing a sulfur-bearing metallic liquid. For these experiments, both solid metal/ liquid silicate and liquid metal/ liquid silicate (LM/LS) partition coefficients are reported (Table 1). In order to isolate the effect of pressure on siderophile element partition coefficients, we have compared our results at high pressures to calculated 1 bar values at the same T and fO(sub)2 as our experiments (based on experiments of [4 - 11]; see results for Ni in Fig. 1; data from [3] and this study). The effect of pressure and other intensive variables on metal-silicate D's can be quantified using the thermodynamically-based relation: lnD (metal/silicate

  5. Study of complexation between two 1,3-alternate calix[4]crown derivatives and alkali metal ions by electrospray ionization mass spectrometry and density functional theory calculations

    NASA Astrophysics Data System (ADS)

    Shamsipur, Mojtaba; Allahyari, Leila; Fasihi, Javad; Taherpour, Avat (Arman); Asfari, Zuhair; Valinejad, Azizollah

    2016-03-01

    Complexation of two 1,3-alternate calix[4]crown ligands with alkali metals (K+, Rb+ and Cs+) has been investigated by electrospray ionization mass spectrometry (ESI-MS) and density functional theory calculations. The binding selectivities of the ligands and the binding constants of their complexes in solution have been determined using the obtained mass spectra. Also the percentage of each formed complex species in the mixture of each ligand and alkali metal has been experimentally evaluated. For both calix[4]crown-5 and calix[4]crown-6 ligands the experimental and theoretical selectivity of their alkali metal complexes found to follow the trend K+ > Rb+ > Cs+. The structures of ligands were optimized by DFT-B3LYP/6-31G method and the structures of complexes were obtained by QM-SCF-MO/PM6 method and discussed in the text.

  6. XPS studies and photocurrent applications of alkali-metals-doped ZnO nanoparticles under visible illumination conditions

    NASA Astrophysics Data System (ADS)

    Saáedi, Abdolhossein; Yousefi, Ramin; Jamali-Sheini, Farid; Zak, Ali Khorsand; Cheraghizade, Mohsen; Mahmoudian, M. R.; Baghchesara, Mohammad Amin; Dezaki, Abbas Shirmardi

    2016-05-01

    The present work is a study about a relationship between X-ray photoelectron spectrometer (XPS) results and photocurrent intensity of alkali-metals-elements doped ZnO nanoparticles, which is carried out under visible illumination conditions. The nanoparticles were synthesized by a simple sol-gel method. Structure and morphology studies of the NPs were carried out by X-ray diffraction analysis (XRD) and transmission electron microscopy (TEM). The effect of doping on the optical band-gap was investigated by using UV-visible spectrometer. The absorption peak of the doped ZnO NPs was red-shifted with respect to that of the undoped ZnO NPs. After that, the photocurrent application of the products was examined under a white light source at 2 V bias. The photocurrent results showed that, the current intensity of the ZnO NPs was increased by doping materials. However, K-doped ZnO NPs showed the highest photocurrent intensity. Finally, a discussion was carried out about the obtained photocurrent results by the O-1s spectra of the XPS of the samples. Our results suggest that the alkali-metals-doped ZnO NPs exhibit considerable promise for highly sensitive visible-light photodetectors.

  7. Influence of alkali metal cations on the thermal, mechanical and morphological properties of rectorite/chitosan bio-nanocomposite films.

    PubMed

    Babul Reddy, A; Jayaramudu, J; Siva Mohan Reddy, G; Manjula, B; Sadiku, E R

    2015-05-20

    The main theme of this work is to study the influence of ion-exchangeable alkali metal cations, such as: Li(+), Na(+), K(+), and Cs(+) on the thermal, mechanical and morphological properties. In this regard, a set of rectorite/chitosan (REC-CS) bio-nanocomposite films (BNCFs) was prepared by facile reaction of chitosan with ion-exchanged REC clay. The microstructure and morphology of BNCFs were investigated with XRD, TEM, SEM and AFM. Thermal and tensile properties of BNCFs were also investigated. As revealed from TEM and XRD results, the BNCFs featured a mixed morphology. Some intercalated clay sheets, together with nano-sized clay tactoids were obtained in LiREC/CS, NaREC/CS and KREC/CS of the BNCFs. From fractured surface study, via SEM, it was observed that the dispersion of chitosan polymer attaches to (and covers) the clay platelets. FTIR confirmed strong hydrogen bonds between clay and chitosan polymer. In addition, the thermal stabilities significantly varied when alkali metal cations varied from Li(+) to Cs(+). The BNCFs featured high tensile strengths (up to 84 MPa) and tensile moduli (up to 45 GPa). After evaluating these properties of BNCFs, we came to conclusion that these bio-nano composites can be used for packaging applications. PMID:25817663

  8. Structural and electronic engineering of 3DOM WO3 by alkali metal doping for improved NO2 sensing performance.

    PubMed

    Wang, Zhihua; Fan, Xiaoxiao; Han, Dongmei; Gu, Fubo

    2016-05-19

    Novel alkali metal doped 3DOM WO3 materials were prepared using a simple colloidal crystal template method. Raman, XRD, SEM, TEM, XPS, PL, Hall and UV-Vis techniques were used to characterize the structural and electronic properties of all the products, while the corresponding sensing performances targeting ppb level NO2 were determined at different working temperatures. For the overall goal of structural and electronic engineering, the co-effect of structural and electronic properties on the improved NO2 sensing performance of alkali metal doped 3DOM WO3 was studied. The test results showed that the gas sensing properties of 3DOM WO3/Li improved the most, with the fast response-recovery time and excellent selectivity. More importantly, the response of 3DOM WO3/Li to 500 ppb NO2 was up to 55 at room temperature (25 °C). The especially high response to ppb level NO2 at room temperature (25 °C) in this work has a very important practical significance. The best sensing performance of 3DOM WO3/Li could be ascribed to the most structure defects and the highest carrier mobility. And the possible gas sensing mechanism based on the model of the depletion layer was proposed to demonstrate that both structural and electronic properties are responsible for the NO2 sensing behavior. PMID:27109698

  9. Molecular origin of high free energy barriers for alkali metal ion transfer through ionic liquid-graphene electrode interfaces.

    PubMed

    Ivaništšev, Vladislav; Méndez-Morales, Trinidad; Lynden-Bell, Ruth M; Cabeza, Oscar; Gallego, Luis J; Varela, Luis M; Fedorov, Maxim V

    2016-01-14

    In this work we study mechanisms of solvent-mediated ion interactions with charged surfaces in ionic liquids by molecular dynamics simulations, in an attempt to reveal the main trends that determine ion-electrode interactions in ionic liquids. We compare the interfacial behaviour of Li(+) and K(+) at a charged graphene sheet in a room temperature ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate, and its mixtures with lithium and potassium tetrafluoroborate salts. Our results show that there are dense interfacial solvation structures in these electrolytes that lead to the formation of high free energy barriers for these alkali metal cations between the bulk and direct contact with the negatively charged surface. We show that the stronger solvation of Li(+) in the ionic liquid leads to the formation of significantly higher interfacial free energy barriers for Li(+) than for K(+). The high free energy barriers observed in our simulations can explain the generally high interfacial resistance in electrochemical storage devices that use ionic liquid-based electrolytes. Overcoming these barriers is the rate-limiting step in the interfacial transport of alkali metal ions and, hence, appears to be a major drawback for a generalised application of ionic liquids in electrochemistry. Some plausible strategies for future theoretical and experimental work for tuning them are suggested. PMID:26661060

  10. Universal scaling of potential energy functions describing intermolecular interactions. II. The halide-water and alkali metal-water interactions

    SciTech Connect

    Werhahn, Jasper C.; Akase, Dai; Xantheas, Sotiris S.

    2014-08-14

    The scaled versions of the newly introduced [S. S. Xantheas and J. C. Werhahn, J. Chem. Phys.141, 064117 (2014)] generalized forms of some popular potential energy functions (PEFs) describing intermolecular interactions – Mie, Lennard-Jones, Morse, and Buckingham exponential-6 – have been used to fit the ab initio relaxed approach paths and fixed approach paths for the halide-water, X-(H2O), X = F, Cl, Br, I, and alkali metal-water, M+(H2O), M = Li, Na, K, Rb, Cs, interactions. The generalized forms of those PEFs have an additional parameter with respect to the original forms and produce fits to the ab initio data that are between one and two orders of magnitude better in the χ2 than the original PEFs. They were found to describe both the long-range, minimum and repulsive wall of the respective potential energy surfaces quite accurately. Overall the 4-parameter extended Morse (eM) and generalized Buckingham exponential-6 (gBe-6) potentials were found to best fit the ab initio data for these two classes of ion-water interactions. Finally, the fitted values of the parameter of the (eM) and (gBe-6) PEFs that control the repulsive wall of the potential correlate remarkably well with the ionic radii of the halide and alkali metal ions.

  11. Alkali metal cation complexation by 1,3-alternate, mono-ionisable calix[4]arene-benzocrown-6 compounds

    DOE PAGESBeta

    Surowiec, Malgorzata A.; Custelcean, Radu; Surowiec, Kazimierz; Bartsch, Richard A.

    2014-04-23

    Alkali metal cation extraction behavior for two series of 1,3-alternate, mono-ionizable calix[4]arene-benzocrown-6 compounds is examined. In Series 1, the proton-ionizable group is a substituent on the benzo group of the polyether ring that directs it away from the crown ether cavity. In Series 2, the proton-ionizable group is attached to one para position in the calixarene framework, thus positioning it over the crown ether ring. Competitive solvent extraction of alkali metal cations from aqueous solutions into chloroform shows high Cs+ efficiency and selectivity. Single-species extraction pH profiles of Cs+ for Series 1 and 2 ligands with the same proton-ionizable groupmore » are very similar. Thus, association of Cs+ with the calixcrown ring is more important than the the proton-ionizable group’s position in relation to the crown ether cavity. Solid-state structures are presented for two unionized ligands from Series 2, as is a crystal containing two different ionized ligand–Cs+ complexes.« less

  12. Alkali metal cation complexation by 1,3-alternate, mono-ionisable calix[4]arene-benzocrown-6 compounds

    SciTech Connect

    Surowiec, Malgorzata A.; Custelcean, Radu; Surowiec, Kazimierz; Bartsch, Richard A.

    2014-04-23

    Alkali metal cation extraction behavior for two series of 1,3-alternate, mono-ionizable calix[4]arene-benzocrown-6 compounds is examined. In Series 1, the proton-ionizable group is a substituent on the benzo group of the polyether ring that directs it away from the crown ether cavity. In Series 2, the proton-ionizable group is attached to one para position in the calixarene framework, thus positioning it over the crown ether ring. Competitive solvent extraction of alkali metal cations from aqueous solutions into chloroform shows high Cs+ efficiency and selectivity. Single-species extraction pH profiles of Cs+ for Series 1 and 2 ligands with the same proton-ionizable group are very similar. Thus, association of Cs+ with the calixcrown ring is more important than the the proton-ionizable group’s position in relation to the crown ether cavity. Solid-state structures are presented for two unionized ligands from Series 2, as is a crystal containing two different ionized ligand–Cs+ complexes.

  13. Use the superconducting proximity effect to investigate alkali metal films and the comparison between the experiment and theory

    NASA Astrophysics Data System (ADS)

    Zhang, Manjiang

    Bilayers of Pb and the alkali metals Cs, Rb, K and Na were quench condensed on the quartz plate. The transition temperature measurement provides information about interface barriers between the Pb and the alkali metals. Such a barrier, which is not due to impurities or oxidation, is particularly large in Pb/Cs sandwiches. The thin K film is forced into an insulating state by being covered with sub-monolayers of Pb. The SPE is used to investigate the electronic change in the alkali film. The K film behaves as if its electrons are unable to carry a current in the x-y-plane but can easily move in the z-direction. This shows on the length scale of the K film thickness, the electronic properties of the film do not change noticeably during the metal-insulator transition. The superconducting proximity effect is investigated for SN-double layers in the thin film limit. In this regime, the normalized initial slope Ssn = (ds=Ts )|dTc=ddn| is independent of the thickness of the superconductor, the mean free path of the films and the transparency of the interface if it is not too small. The transition temperature Tc is compared with a numerical calculation developed in our group. The deviation between the experiment and theory decreases from the normal metal to the superconductor with a relative high transition temperature. The deviation factor decreases from 2.5 for Cu, Ag, Au, Mg to 1.5 for Cd, Zn, Al and finally no disagreement for In and Sn. A weak perpendicular magnetic field is applied on the super- and normal conductor double layers. The difference of the transition temperature dTc measured with and without magnetic field increases with increasing the normal metal thickness. A quantitative explanation is given based on the increased dephasing of the electrons in the magnetic field. Numerical calculation of the transition temperature based on the strong coupling theory is also given and compared with the experimental results.

  14. 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. PMID:26650573

  15. Alkali metal, alkaline earth metal, and ammonium ion selectivities of dibenzo-16-crown-5 compounds with functional side arms in ion-selective electrodes

    SciTech Connect

    Ohki, Akira; Lu, J.P.; Huang, X.; Bartsch, R.A. )

    1994-12-01

    Potentiometric selectivities of 11 dibenzo-16-crown-5 compounds for alkali metal, alkaline earth metal, and ammonium ions have been determined in solvent polymeric membrane electrodes. The ionophores bear one or two pendent groups on the central carbon of the three-carbon bridge in the polyether ring. Side-arm variation includes OCH[sub 3], OCH[sub 2]CH[sub 2]OCH[sub 3], OCH[sub 2]CO[sub 2]C[sub 2]H[sub 5], OCH[sub 2]C(O)N(C[sub 2]H[sub 5])[sub 2], and OCH[sub 2]C(O)N(C[sub 5]H[sub 11])[sub 2] units. Attachment of a propyl group to the ring carbon that bears an extended, oxygen-containing side arm increases the selectivity for Na[sup +] relative to larger alkali metal and alkaline earth metal cations. For a given side arm, a linear relationship is obtained when the enhancement in Na[sup +] selectivity produced by attachment of a geminal propyl group is plotted against the diameter of the interference ion. Potentiometric responses of the dibenzo-16-crown-5 compounds are rationalized in terms of the crown ether ring size and the oxygen basicity, conformational positioning, and rigidity of the side arm. 22 refs., 3 figs., 2 tabs.

  16. Partitioning of Mo, P and other siderophile elements (Cu, Ga, Sn, Ni, Co, Cr, Mn, V, and W) between metal and silicate melt as a function of temperature and silicate melt composition

    NASA Astrophysics Data System (ADS)

    Righter, K.; Pando, K. M.; Danielson, L.; Lee, Cin-Ty

    2010-03-01

    Metal-silicate partition coefficients can provide information about the earliest differentiation histories of terrestrial planets and asteroids. Systematic studies of the effects of key parameters such as temperature and melt composition are lacking for many elements. In particular, data for Mo is scarce, but given its refractory nature, is of great value in interpreting metal-silicate equilibrium. Two series of experiments have been carried out to study Mo and P partitioning between Fe metallic liquid and basaltic to peridotitic silicate melt, at 1 GPa and temperatures between 1500 and 1900 °C. Because the silicate melt utilized was natural basalt, there are also measurable quantities of 9 other siderophile elements (Ni, Co, W, Sn, Cu, Mn, V, Cr, Ga and Zn). The Ni and Co data can be used to assess consistency with previous studies. In addition, the new data also allow a first systematic look at the temperature dependence of Cu, Ga, Sn, Cr, Mn V and W for basaltic to peridotitic melts. Many elements exhibit an increase in siderophile behavior at higher temperature, contrary to popular belief, but consistent with predictions from thermodynamics. Using these new data we examine DMomet/sil and DPmet/sil in detail and show that increasing temperature causes a decrease in the former and an increase in the latter, whereas both increase with MgO content of the silicate melt. The depletions of Mo and P in the mantle of the Earth can be explained by metal-silicate equilibrium at magma ocean conditions — both elements are satisfied at PT conditions of an intermediate depth magma ocean for the Earth 22.5 GPa and 2400 °C.

  17. Comparisons between adsorption and diffusion of alkali, alkaline earth metal atoms on silicene and those on silicane: Insight from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Bo, Xu; Huan-Sheng, Lu; Bo, Liu; Gang, Liu; Mu-Sheng, Wu; Chuying, Ouyang

    2016-06-01

    The adsorption and diffusion behaviors of alkali and alkaline-earth metal atoms on silicane and silicene are both investigated by using a first-principles method within the frame of density functional theory. Silicane is staler against the metal adatoms than silicene. Hydrogenation makes the adsorption energies of various metal atoms considered in our calculations on silicane significantly lower than those on silicene. Similar diffusion energy barriers of alkali metal atoms on silicane and silicene could be observed. However, the diffusion energy barriers of alkali-earth metal atoms on silicane are essentially lower than those on silicene due to the small structural distortion and weak interaction between metal atoms and silicane substrate. Combining the adsorption energy with the diffusion energy barriers, it is found that the clustering would occur when depositing metal atoms on perfect hydrogenated silicene with relative high coverage. In order to avoid forming a metal cluster, we need to remove the hydrogen atoms from the silicane substrate to achieve the defective silicane. Our results are helpful for understanding the interaction between metal atoms and silicene-based two-dimensional materials. Project supported by the Natural Science Foundation of Jiangxi Province, China (Grant Nos. 20152ACB21014, 20151BAB202006, and 20142BAB212002) and the Fund from the Jiangxi Provincial Educational Committee, China (Grant No. GJJ14254). Bo Xu is also supported by the Oversea Returned Project from the Ministry of Education, China.

  18. Experimental determination of Fe isotope fractionation between liquid metal, silicate and sulfide at high pressures and temperatures

    NASA Astrophysics Data System (ADS)

    Williams, H. M.; Wood, B. J.; Halliday, A. N.

    2007-12-01

    There is evidence for significant equilibrium Fe isotope fractionation (≤0.26‰/amu) between metal and troilite (FeS) in iron meteorites (Williams et al., EPSL (250) 2006) and a smaller fractionation (<0.1‰/amu) between metal and olivine in pallasites (Zhu et al., EPSL (200) 2002; Weyer et al., EPSL (240) 2005). Theory suggests that differences in iron oxidation state and coordination between metal, silicate and FeS will result in stable isotope fractionation (Polyakov and Mineev, GCA (64) 2000; Schauble et al., GCA (65) 2001). However, it is not yet clear if the apparent observed fractionations can be extrapolated to the pressure and temperature conditions of planetary core formation. We have investigated Fe isotope fractionation between silicate melt and liquid Fe-S alloys and between liquid iron and basaltic melt at pressure and temperature conditions of 2-2.5GPa and 1920-2150K using piston-cylinder partitioning experiments from previous studies (Kilburn and Wood EPSL (152) 1997; Gessmann and Wood, EPSL (200) 2002; Wood et al., EPSL (in revision) 2007). Metal, sulfide and silicate fractions were separated from mounted and sectioned experimental charges using a computer-controlled micromill (New Wave-Merchantek). Sample dissolution, Fe purification and isotopic analysis followed established procedures (Williams et al., EPSL (235) 2005). In agreement with another preliminary high-pressure experimental study (Poitrasson and Roskosz, LPSC XXXVIII 2007) we find no appreciable fractionation between liquid iron metal and basaltic melt. However, there is a resolvable Fe isotope fractionation between silicate melt and Fe-S alloy which ranges from 0.12±0.04 to 0.15±0.04‰/amu for separate experiments (errors are propagated based on the 2 SD errors of replicate analyses). The Fe isotope compositions of coexisting phases from these experiments define a positive linear relationship with a slope that is, within error, equal to unity, implying isotopic equilibrium. No

  19. On-sun test results from second-generation and advanced-concepts alkali-metal pool-boiler receivers

    SciTech Connect

    Moreno, J.B.; Andraka, C.E.; Moss, T.A.; Cordeiro, P.G.; Dudley, V.E.; Rawlinson, K.S.

    1994-05-01

    Two 75-kW{sub t} alkali-metal pool-boiler solar receivers have been successfully tested at Sandia National Laboratories` National Solar Thermal Test Facility. The first one, Sandia`s `` second-generation pool-boiler receiver,`` was designed to address commercialization issues identified during post-test assessment of Sandia`s first-generation pool-boiler receiver. It was constructed from Haynes alloy 230 and contained the alkali-metal alloy NaK-78. The absorber`s wetted side had a brazed-on powder-metal coating to stabilize boiling. This receiver was evaluated for boiling stability, hot- and warm-restart behavior, and thermal efficiency. Boiling was stable under all conditions. All of the hot restarts were successful. Mild transient hot spots observed during some hot restarts were eliminated by the addition of 1/3 torr of xenon to the vapor space. All of the warm restarts were also successful. The heat-transfer crisis that damaged the first receiver did not recur. Thermal efficiency was 92.3% at 750{degrees}C with 69.6 kW{sub t} solar input. The second receiver tested, Sandia`s ``advanced-concepts receiver,`` was a replica of the first-generation receiver except that the cavities, which were electric-discharge-machined in the absorber for boiling stability, were eliminated. This step was motivated by bench-scale test results that showed that boiling stability improved with increased heated-surface area, tilt of the heated surface from vertical, and added xenon. The bench-scale results suggested that stable boiling might be possible without heated-surface modification in a 75-kW{sub t} receiver. Boiling in the advanced-concepts receiver with 1/3 torr of xenon added has been stable under all conditions, confirming the bench-scale tests.

  20. A curious interplay in the films of N-heterocyclic carbene PtII complexes upon deposition of alkali metals

    NASA Astrophysics Data System (ADS)

    Makarova, Anna A.; Grachova, Elena V.; Niedzialek, Dorota; Solomatina, Anastasia I.; Sonntag, Simon; Fedorov, Alexander V.; Vilkov, Oleg Yu.; Neudachina, Vera S.; Laubschat, Clemens; Tunik, Sergey P.; Vyalikh, Denis V.

    2016-05-01

    The recently synthesized series of PtII complexes containing cyclometallating (phenylpyridine or benzoquinoline) and N-heterocyclic carbene ligands possess intriguing structures, topologies, and light emitting properties. Here, we report curious physicochemical interactions between in situ PVD-grown films of a typical representative of the aforementioned PtII complex compounds and Li, Na, K and Cs atoms. Based on a combination of detailed core-level photoelectron spectroscopy and quantum-chemical calculations at the density functional theory level, we found that the deposition of alkali atoms onto the molecular film leads to unusual redistribution of electron density: essential modification of nitrogen sites, reduction of the coordination PtII centre to Pt0 and decrease of electron density on the bromine atoms. A possible explanation for this is formation of a supramolecular system “Pt complex-alkali metal ion” the latter is supported by restoration of the system to the initial state upon subsequent oxygen treatment. The discovered properties highlight a considerable potential of the PtII complexes for a variety of biomedical, sensing, chemical, and electronic applications.

  1. A curious interplay in the films of N-heterocyclic carbene PtII complexes upon deposition of alkali metals

    PubMed Central

    Makarova, Anna A.; Grachova, Elena V.; Niedzialek, Dorota; Solomatina, Anastasia I.; Sonntag, Simon; Fedorov, Alexander V.; Vilkov, Oleg Yu.; Neudachina, Vera S.; Laubschat, Clemens; Tunik, Sergey P.; Vyalikh, Denis V.

    2016-01-01

    The recently synthesized series of PtII complexes containing cyclometallating (phenylpyridine or benzoquinoline) and N-heterocyclic carbene ligands possess intriguing structures, topologies, and light emitting properties. Here, we report curious physicochemical interactions between in situ PVD-grown films of a typical representative of the aforementioned PtII complex compounds and Li, Na, K and Cs atoms. Based on a combination of detailed core-level photoelectron spectroscopy and quantum-chemical calculations at the density functional theory level, we found that the deposition of alkali atoms onto the molecular film leads to unusual redistribution of electron density: essential modification of nitrogen sites, reduction of the coordination PtII centre to Pt0 and decrease of electron density on the bromine atoms. A possible explanation for this is formation of a supramolecular system “Pt complex-alkali metal ion”; the latter is supported by restoration of the system to the initial state upon subsequent oxygen treatment. The discovered properties highlight a considerable potential of the PtII complexes for a variety of biomedical, sensing, chemical, and electronic applications. PMID:27151364

  2. Thermal and optical properties of Nd3+ doped lead zinc borate glasses—Influence of alkali metal ions

    NASA Astrophysics Data System (ADS)

    Sasi Kumar, M. V.; Rajesh, D.; Balakrishna, A.; Ratnakaram, Y. C.

    2013-04-01

    In the present investigation a new series of six different Nd3+ doped alkali and mixed alkali (Li, Na, K, Li-Na, Li-K and Na-K) heavy metal (PbO and ZnO) borate glasses were prepared using the melt quenching technique. The amorphous nature of the glass systems has been identified based on the X-ray diffraction analysis. The glass transition studies were carried out using differential scanning calorimetry (DSC). Optical properties were studied by measuring the optical absorption and near infrared luminescence spectra. The Judd-Ofelt (J-O) theory has been applied to calculate J-O intensity parameters, Ωλ (λ=2, 4 and 6) and in turn used to estimate radiative properties of certain transitions. Spectroscopic parameters such as transition probabilities (AT), branching ratios (β), radiative lifetimes (τR) and integrated absorption cross-sections (Σ) were calculated using J-O intensity parameters for all transitions. Using emission spectra, experimental branching ratios and stimulated emission cross-sections (σP) are obtained for all the observed emission transitions.

  3. A curious interplay in the films of N-heterocyclic carbene Pt(II) complexes upon deposition of alkali metals.

    PubMed

    Makarova, Anna A; Grachova, Elena V; Niedzialek, Dorota; Solomatina, Anastasia I; Sonntag, Simon; Fedorov, Alexander V; Vilkov, Oleg Yu; Neudachina, Vera S; Laubschat, Clemens; Tunik, Sergey P; Vyalikh, Denis V

    2016-01-01

    The recently synthesized series of Pt(II) complexes containing cyclometallating (phenylpyridine or benzoquinoline) and N-heterocyclic carbene ligands possess intriguing structures, topologies, and light emitting properties. Here, we report curious physicochemical interactions between in situ PVD-grown films of a typical representative of the aforementioned Pt(II) complex compounds and Li, Na, K and Cs atoms. Based on a combination of detailed core-level photoelectron spectroscopy and quantum-chemical calculations at the density functional theory level, we found that the deposition of alkali atoms onto the molecular film leads to unusual redistribution of electron density: essential modification of nitrogen sites, reduction of the coordination Pt(II) centre to Pt(0) and decrease of electron density on the bromine atoms. A possible explanation for this is formation of a supramolecular system "Pt complex-alkali metal ion"; the latter is supported by restoration of the system to the initial state upon subsequent oxygen treatment. The discovered properties highlight a considerable potential of the Pt(II) complexes for a variety of biomedical, sensing, chemical, and electronic applications. PMID:27151364

  4. Sub-Shot-Noise Magnetometry with a Correlated Spin-Relaxation Dominated Alkali-Metal Vapor

    SciTech Connect

    Kominis, I. K.

    2008-02-22

    Spin noise sets fundamental limits to the precision of measurements using spin-polarized atomic vapors, such as performed with sensitive atomic magnetometers. Spin squeezing offers the possibility to extend the measurement precision beyond the standard quantum limit of uncorrelated atoms. Contrary to current understanding, we show that, even in the presence of spin relaxation, spin squeezing can lead to a significant reduction of spin noise, and hence an increase in magnetometric sensitivity, for a long measurement time. This is the case when correlated spin relaxation due to binary alkali-atom collisions dominates independently acting decoherence processes, a situation realized in thermal high atom-density magnetometers and clocks.

  5. Measurement method for the nuclear anapole moment of laser-trapped alkali-metal atoms

    SciTech Connect

    Gomez, E.; Aubin, S.; Sprouse, G. D.; Orozco, L. A.; DeMille, D. P.

    2007-03-15

    Weak interactions within a nucleus generate a nuclear spin dependent, parity-violating electromagnetic moment, the anapole moment. We analyze a method to measure the nuclear anapole moment through the electric dipole transition it induces between hyperfine states of the ground level. The method requires tight confinement of the atoms to position them at the antinode of a standing wave Fabry-Perot cavity driving the anapole-induced microwave E1 transition. We explore the necessary limits in the number of atoms, excitation fields, trap type, interrogation method, and systematic tests necessary for such measurements in francium, the heaviest alkali.

  6. A Quantitative Tunneling/Desorption Model for the Exchange Current at the Porous Electrode/Beta - Alumina/Alkali Metal Gas Three Phase Zone at 700-1300K

    NASA Technical Reports Server (NTRS)

    Williams, R. M.; Ryan, M. A.; Saipetch, C.; LeDuc, H. G.

    1996-01-01

    The exchange current observed at porous metal electrodes on sodium or potassium beta -alumina solid electrolytes in alkali metal vapor is quantitatively modeled with a multi-step process with good agreement with experimental results.

  7. Selective removal of alkali metal cations from multiply-charged ions via gas-phase ion/ion reactions using weakly coordinating anions.

    PubMed

    Luongo, Carl A; Bu, Jiexun; Burke, Nicole L; Gilbert, Joshua D; Prentice, Boone M; Cummings, Steven; Reed, Christopher A; McLuckey, Scott A

    2015-03-01

    Selective removal of alkali metal cations from mixed cation multiply-charged peptide ions is demonstrated here using gas-phase ion/ion reactions with a series of weakly coordinating anions (WCAs), including hexafluorophosphate (PF6 (-)), tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BARF), tetrakis(pentafluorophenyl)borate (TPPB), and carborane (CHB11Cl11 (-)). In all cases, a long-lived complex is generated by dication/anion condensation followed by ion activation to compare proton transfer with alkali ion transfer from the peptide to the anion. The carborane anion was the only anion studied to undergo dissociation exclusively through loss of the metallated anion, regardless of the studied metal adduct. All other anions studied yield varying abundances of protonated and metallated peptide depending on the peptide sequence and the metal identity. Density functional theory calculations suggest that for the WCAs studied, metal ion transfer is most strongly favored thermodynamically, which is consistent with the experimental results. The carborane anion is demonstrated to be a robust reagent for the selective removal of alkali metal cations from peptide cations with mixtures of excess protons and metal cations. PMID:25560986

  8. Selective Removal of Alkali Metal Cations from Multiply-Charged Ions via Gas-Phase Ion/Ion Reactions Using Weakly Coordinating Anions

    NASA Astrophysics Data System (ADS)

    Luongo, Carl A.; Bu, Jiexun; Burke, Nicole L.; Gilbert, Joshua D.; Prentice, Boone M.; Cummings, Steven; Reed, Christopher A.; McLuckey, Scott A.

    2015-03-01

    Selective removal of alkali metal cations from mixed cation multiply-charged peptide ions is demonstrated here using gas-phase ion/ion reactions with a series of weakly coordinating anions (WCAs), including hexafluorophosphate (PF6 -), tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BARF), tetrakis(pentafluorophenyl)borate (TPPB), and carborane (CHB11Cl11 -). In all cases, a long-lived complex is generated by dication/anion condensation followed by ion activation to compare proton transfer with alkali ion transfer from the peptide to the anion. The carborane anion was the only anion studied to undergo dissociation exclusively through loss of the metallated anion, regardless of the studied metal adduct. All other anions studied yield varying abundances of protonated and metallated peptide depending on the peptide sequence and the metal identity. Density functional theory calculations suggest that for the WCAs studied, metal ion transfer is most strongly favored thermodynamically, which is consistent with the experimental results. The carborane anion is demonstrated to be a robust reagent for the selective removal of alkali metal cations from peptide cations with mixtures of excess protons and metal cations.

  9. Metal-Silicate Partitioning of Bi, In, and Cd as a Function of Temperature and Melt Composition

    NASA Technical Reports Server (NTRS)

    Marin, Nicole; Righter, K.; Danielson, L.; Pando, K.; Lee, C.

    2013-01-01

    The origin of volatile elements in the Earth, Moon and Mars is not known; however, several theories have been proposed based on volatile elements such as In, As, Se, Te and Zn which are in lower concentration in the Earth, Moon, and Mars than in chondrites. Explanations for these low concentrations are based on two contrasting theories for the origin of Earth: equilibrium core formation versus late accretion. One idea is that the volatiles were added during growth of the planets and Moon, and some mobilized into the metallic core while others stayed in the mantle (e.g., [1]). The competing idea is that they were added to the mantles after core formation had completed (e.g., [2]). Testing these ideas involves quantitative modeling which can only be performed after data is obtained on the systematic metal-silicate partitioning behavior of volatile elements with temperature, pressure and melt composition. Until now, such data for Bi, In, and Cd has been lacking. After conducting a series of high pressure, high temperature experiments, the metal-silicate partition coefficients of Bi, In, and Cd as a function of temperature and melt composition can be used to evaluate potential conditions under which terrestrial planets differentiated into core and mantle, and how they acquired volatiles.

  10. Estimates of the relative magnitudes of the isotropic and anisotropic magnetic-dipole hyperfine interactions in alkali-metal-noble-gas systems

    NASA Astrophysics Data System (ADS)

    Walter, D. K.; Happer, W.; Walker, T. G.

    1998-11-01

    We present a detailed theoretical analysis of the noble-gas nuclear-spin relaxation due to the anisotropic magnetic-dipole hyperfine interaction between the noble-gas nucleus and alkali-metal valence electron vis à vis the already well-understood (spin-conserving) isotropic magnetic-dipole hyperfine interaction in alkali-metal-noble-gas systems. We find that, for all pairs in which the noble gas is not helium, the predicted spin-relaxation rate from the anisotropic interaction does not exceed 2.5% of the rate from the isotropic interaction, thereby not appreciably limiting the maximum noble-gas nuclear polarization attainable via spin-exchange collisions with polarized alkali-metal atoms. For alkali-metal-helium pairs, we predict that the anisotropic interaction has a slightly larger relative effect, perhaps limiting the nuclear polarization to ~95% of the electronic polarization in the Rb-3He system; however, our confidence in the helium results is limited by a lack of knowledge of the interatomic potentials necessary for the calculation.

  11. MS/MS and LC-MS/MS analysis of choline/ethanolamine plasmalogens via promotion of alkali metal adduct formation.

    PubMed

    Otoki, Yurika; Nakagawa, Kiyotaka; Kato, Shunji; Miyazawa, Teruo

    2015-11-01

    Tandem mass spectrometry (MS/MS) has been used for the analysis of plasmalogen (Pls), a physiologically important class of vinyl ether-linked phospholipid. However, MS/MS generally causes little fragmentation of Pls, especially choline Pls (PC-Pls). Previous MS/MS studies reported an increased formation of product ions of PC-Pls (and also ethanolamine Pls (PE-Pls)) in the presence of 'alkali metals.' Therefore, use of alkali metals considerably leads to the development of a method for analysis of both PC- and PE-Pls. In this study, this notion was evaluated using quadrupole-time-of-flight MS/MS and liquid chromatography (LC) coupled with MS/MS. Results from MS/MS confirmed that alkali metals (e.g., sodium) produced significant fragmentation of PC-Pls and PE-Pls. A number of structure-diagnostic product ions exhibiting high intensities were observed under optimized MS/MS conditions using alkali metals. Moreover, the ability to selectively and sensitively identify PC-Pls and PE-Pls at the molecular species level in biological samples (rat brain and heart) was demonstrated using LC-MS/MS. Therefore, the herein developed method appears to be a powerful tool for analyzing Pls and may provide a better understanding of their physiological roles in vivo. PMID:26447938

  12. Crown-Ether Derived Graphene Hybrid Composite for Membrane-Free Potentiometric Sensing of Alkali Metal Ions.

    PubMed

    Olsen, Gunnar; Ulstrup, Jens; Chi, Qijin

    2016-01-13

    We report the design and synthesis of newly functionalized graphene hybrid material that can be used for selective membrane-free potentiometric detection of alkali metal ions, represented by potassium ions. Reduced graphene oxide (RGO) functionalized covalently by 18-crown[6] ether with a dense surface coverage is achieved by the introduction of a flexible linking molecule. The resulting hybrid composite is highly stable and is capable of detecting potassium ions down to micromolar ranges with a selectivity over other cations (including Ca(2+), Li(+), Na(+), NH4(+)) at concentrations up to 25 mM. This material can be combined further with disposable chips, demonstrating its promise as an effective ion-selective sensing component for practical applications. PMID:26703780

  13. Hyperfine-induced quadrupole moments of alkali-metal-atom ground states and their implications for atomic clocks

    NASA Astrophysics Data System (ADS)

    Derevianko, Andrei

    2016-01-01

    Spherically symmetric ground states of alkali-metal atoms do not posses electric quadrupole moments. However, the hyperfine interaction between nuclear moments and atomic electrons distorts the spherical symmetry of electronic clouds and leads to nonvanishing atomic quadrupole moments. We evaluate these hyperfine-induced quadrupole moments using techniques of relativistic many-body theory and compile results for Li, Na, K, Rb, and Cs atoms. For heavy atoms we find that the hyperfine-induced quadrupole moments are strongly (two orders of magnitude) enhanced by correlation effects. We further apply the results of the calculation to microwave atomic clocks where the coupling of atomic quadrupole moments to gradients of electric fields leads to clock frequency uncertainties. We show that for 133Cs atomic clocks, the spatial gradients of electric fields must be smaller than 30 V /cm2 to guarantee fractional inaccuracies below 10-16.

  14. Structural and electronic engineering of 3DOM WO3 by alkali metal doping for improved NO2 sensing performance

    NASA Astrophysics Data System (ADS)

    Wang, Zhihua; Fan, Xiaoxiao; Han, Dongmei; Gu, Fubo

    2016-05-01

    Novel alkali metal doped 3DOM WO3 materials were prepared using a simple colloidal crystal template method. Raman, XRD, SEM, TEM, XPS, PL, Hall and UV-Vis techniques were used to characterize the structural and electronic properties of all the products, while the corresponding sensing performances targeting ppb level NO2 were determined at different working temperatures. For the overall goal of structural and electronic engineering, the co-effect of structural and electronic properties on the improved NO2 sensing performance of alkali metal doped 3DOM WO3 was studied. The test results showed that the gas sensing properties of 3DOM WO3/Li improved the most, with the fast response-recovery time and excellent selectivity. More importantly, the response of 3DOM WO3/Li to 500 ppb NO2 was up to 55 at room temperature (25 °C). The especially high response to ppb level NO2 at room temperature (25 °C) in this work has a very important practical significance. The best sensing performance of 3DOM WO3/Li could be ascribed to the most structure defects and the highest carrier mobility. And the possible gas sensing mechanism based on the model of the depletion layer was proposed to demonstrate that both structural and electronic properties are responsible for the NO2 sensing behavior.Novel alkali metal doped 3DOM WO3 materials were prepared using a simple colloidal crystal template method. Raman, XRD, SEM, TEM, XPS, PL, Hall and UV-Vis techniques were used to characterize the structural and electronic properties of all the products, while the corresponding sensing performances targeting ppb level NO2 were determined at different working temperatures. For the overall goal of structural and electronic engineering, the co-effect of structural and electronic properties on the improved NO2 sensing performance of alkali metal doped 3DOM WO3 was studied. The test results showed that the gas sensing properties of 3DOM WO3/Li improved the most, with the fast response-recovery time and

  15. Alkali Metal Halide Salts as Interface Additives to Fabricate Hysteresis-Free Hybrid Perovskite-Based Photovoltaic Devices.

    PubMed

    Wang, Lili; Moghe, Dhanashree; Hafezian, Soroush; Chen, Pei; Young, Margaret; Elinski, Mark; Martinu, Ludvik; Kéna-Cohen, Stéphane; Lunt, Richard R

    2016-09-01

    A new method was developed for doping and fabricating hysteresis-free hybrid perovskite-based photovoltaic devices by using alkali metal halide salts as interface layer additives. Such salt layers introduced at the perovskite interface can provide excessive halide ions to fill vacancies formed during the deposition and annealing process. A range of solution-processed halide salts were investigated. The highest performance of methylammonium lead mixed-halide perovskite device was achieved with a NaI interlayer and showed a power conversion efficiency of 12.6% and a hysteresis of less than 2%. This represents a 90% improvement compared to control devices without this salt layer. Through depth-resolved mass spectrometry, optical modeling, and photoluminescence spectroscopy, this enhancement is attributed to the reduction of iodide vacancies, passivation of grain boundaries, and improved hole extraction. Our approach ultimately provides an alternative and facile route to high-performance and hysteresis-free perovskite solar cells. PMID:27532662

  16. Synthesis and X-ray Characterization of Alkali Metal 2-Acyl-1,1,3,3-tetracyanopropenides.

    PubMed

    Karpov, Sergey V; Grigor'ev, Arthur A; Kayukov, Yakov S; Karpova, Irina V; Nasakin, Oleg E; Tafeenko, Victor A

    2016-08-01

    A novel route for synthesis of 2-acyl-1,1,3,3-tetracyanopropenides (ATCN) salts in high yields and excellent purities starting from readily available methyl ketones, malononitrile, bromine, and alkali metal acetates is reported. The starting aryl(heteroaryl) methyl ketones were oxidized to the corresponding α-ketoaldehydes by new a DMSO-NaBr-H2SO4 oxidation system in yields up to 90% within a short reaction time of 8-10 min. The subsequent stages of ATCN preparation are realized in aqueous media without use of any toxic solvents, in accordance with principle 5 of "green chemistry". Lithium, sodium, potassium, rubidium, and cesium 2-benzoyl-1,1,3,3-tetracyanopropenides were characterized by X-ray diffraction analysis. These salts show a good potential for synthesis of five- and six-membered heterocycles and may serve as potentially useful ligands in coordination and supramolecular chemistry. PMID:27384963

  17. Measuring the spin polarization of alkali-metal atoms using nuclear magnetic resonance frequency shifts of noble gases

    SciTech Connect

    Liu, X. H.; Luo, H.; Qu, T. L. Yang, K. Y.; Ding, Z. C.

    2015-10-15

    We report a novel method of measuring the spin polarization of alkali-metal atoms by detecting the NMR frequency shifts of noble gases. We calculated the profile of {sup 87}Rb D1 line absorption cross sections. We then measured the absorption profile of the sample cell, from which we calculated the {sup 87}Rb number densities at different temperatures. Then we measured the frequency shifts resulted from the spin polarization of the {sup 87}Rb atoms and calculated its polarization degrees at different temperatures. The behavior of frequency shifts versus temperature in experiment was consistent with theoretical calculation, which may be used as compensative signal for the NMRG closed-loop control system.

  18. One- and two-photon spectroscopy of highly excited states of alkali-metal atoms on helium nanodroplets

    SciTech Connect

    Pifrader, Alexandra; Allard, Olivier; Auboeck, Gerald; Callegari, Carlo; Ernst, Wolfgang E.; Huber, Robert; Ancilotto, Francesco

    2010-10-28

    Alkali-metal atoms captured on the surface of superfluid helium droplets are excited to high energies ({approx_equal}3 eV) by means of pulsed lasers, and their laser-induced-fluorescence spectra are recorded. We report on the one-photon excitation of the (n+1)p(leftarrow)ns transition of K, Rb, and Cs (n=4, 5, and 6, respectively) and on the two-photon one-color excitation of the 5d(leftarrow)5s transition of Rb. Gated-photon-counting measurements are consistent with the relaxation rates of the bare atoms, hence consistent with the reasonable expectation that atoms quickly desorb from the droplet and droplet-induced relaxation need not be invoked.

  19. Development of processes for the production of solar grade silicon from halides and alkali metals, phase 1 and phase 2

    NASA Technical Reports Server (NTRS)

    Dickson, C. R.; Gould, R. K.; Felder, W.

    1981-01-01

    High temperature reactions of silicon halides with alkali metals for the production of solar grade silicon are described. Product separation and collection processes were evaluated, measure heat release parameters for scaling purposes and effects of reactants and/or products on materials of reactor construction were determined, and preliminary engineering and economic analysis of a scaled up process were made. The feasibility of the basic process to make and collect silicon was demonstrated. The jet impaction/separation process was demonstrated to be a purification process. The rate at which gas phase species from silicon particle precursors, the time required for silane decomposition to produce particles, and the competing rate of growth of silicon seed particles injected into a decomposing silane environment were determined. The extent of silane decomposition as a function of residence time, temperature, and pressure was measured by infrared absorption spectroscopy. A simplistic model is presented to explain the growth of silicon in a decomposing silane enviroment.

  20. Purification and Characterization of an Extracellular, Thermo-Alkali-Stable, Metal Tolerant Laccase from Bacillus tequilensis SN4

    PubMed Central

    Sondhi, Sonica; Sharma, Prince; Saini, Shilpa; Puri, Neena; Gupta, Naveen

    2014-01-01

    A novel extracellular thermo-alkali-stable laccase from Bacillus tequilensis SN4 (SN4LAC) was purified to homogeneity. The laccase was a monomeric protein of molecular weight 32 KDa. UV-visible spectrum and peptide mass fingerprinting results showed that SN4LAC is a multicopper oxidase. Laccase was active in broad range of phenolic and non-phenolic substrates. Catalytic efficiency (kcat/Km) showed that 2, 6-dimethoxyphenol was most efficiently oxidized by the enzyme. The enzyme was inhibited by conventional inhibitors of laccase like sodium azide, cysteine, dithiothreitol and β-mercaptoethanol. SN4LAC was found to be highly thermostable, having temperature optimum at 85°C and could retain more than 80% activity at 70°C for 24 h. The optimum pH of activity for 2, 6-dimethoxyphenol, 2, 2′-azino bis[3-ethylbenzthiazoline-6-sulfonate], syringaldazine and guaiacol was 8.0, 5.5, 6.5 and 8.0 respectively. Enzyme was alkali-stable as it retained more than 75% activity at pH 9.0 for 24 h. Activity of the enzyme was significantly enhanced by Cu2+, Co2+, SDS and CTAB, while it was stable in the presence of halides, most of the other metal ions and surfactants. The extracellular nature and stability of SN4LAC in extreme conditions such as high temperature, pH, heavy metals, halides and detergents makes it a highly suitable candidate for biotechnological and industrial applications. PMID:24871763