WorldWideScience

Sample records for alkali metals phase

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

    Energy Technology Data Exchange (ETDEWEB)

    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. IRMPD Action Spectroscopy of Alkali Metal Cation-Cytosine Complexes: Effects of Alkali Metal Cation Size on Gas Phase Conformation

    NARCIS (Netherlands)

    Yang, B.; Wu, R.R.; Polfer, N.C.; Berden, G.; Oomens, J.; Rodgers, M.T.

    2013-01-01

    The gas-phase structures of alkali metal cation-cytosine complexes generated by electrospray ionization are probed via infrared multiple photon dissociation (IRMPD) action spectroscopy and theoretical calculations. IRMPD action spectra of five alkali metal cation-cytosine complexes exhibit both simi

  3. IRMPD action spectroscopy of alkali metal cation-cytosine complexes: effects of alkali metal cation size on gas phase conformation.

    Science.gov (United States)

    Yang, Bo; Wu, R R; Polfer, N C; Berden, G; Oomens, J; Rodgers, M T

    2013-10-01

    The gas-phase structures of alkali metal cation-cytosine complexes generated by electrospray ionization are probed via infrared multiple photon dissociation (IRMPD) action spectroscopy and theoretical calculations. IRMPD action spectra of five alkali metal cation-cytosine complexes exhibit both similar and distinctive spectral features over the range of ~1000-1900 cm(-1). The IRMPD spectra of the Li(+)(cytosine), Na(+)(cytosine), and K(+)(cytosine) complexes are relatively simple but exhibit changes in the shape and shifts in the positions of several bands that correlate with the size of the alkali metal cation. The IRMPD spectra of the Rb(+)(cytosine) and Cs(+)(cytosine) complexes are much richer as distinctive new IR bands are observed, and the positions of several bands continue to shift in relation to the size of the metal cation. The measured IRMPD spectra are compared to linear IR spectra of stable low-energy tautomeric conformations calculated at the B3LYP/def2-TZVPPD level of theory to identify the conformations accessed in the experiments. These comparisons suggest that the evolution in the features in the IRMPD action spectra with the size of the metal cation, and the appearance of new bands for the larger metal cations, are the result of the variations in the intensities at which these complexes can be generated and the strength of the alkali metal cation-cytosine binding interaction, not the presence of multiple tautomeric conformations. Only a single tautomeric conformation is accessed for all five alkali metal cation-cytosine complexes, where the alkali metal cation binds to the O2 and N3 atoms of the canonical amino-oxo tautomer of cytosine, M(+)(C1).

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

    Science.gov (United States)

    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 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.

  5. Upgrading platform using alkali metals

    Energy Technology Data Exchange (ETDEWEB)

    Gordon, John Howard

    2017-01-17

    A method for removing sulfur, nitrogen or metals from an oil feedstock. 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.

  6. Upgrading platform using alkali metals

    Energy Technology Data Exchange (ETDEWEB)

    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.

  7. Calculation of Interaction Parameters from Immiscible Phase Diagram of Alkali Metal or Alkali Earth Metal-Halide System by Means of Subregular Solution Model

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    In this paper, the interaction parameters in the subregular solution model, λ1 and λ2, are regarded as a linear function of temperature, T. Therefore, the molar excess Gibbs energy of A-B binary system may be reexpressed as follows: The calculation of the model parameters, λ11, λ12, λ21 and λ22, was carried out numerically from the phase diagrams for 11 alkali metal-alkali halide or alkali earth metal-halide systems.In addition, artificial neural network trained by known data has been used to predict the values of these model parameters. The predicted results are in good agreement with the.calculated ones. The applicability of the subregular solution model to the alkali metal-alkali halide or alkali earth metal-halide systems were tested by comparing the available experimental composition along the boundary of miscibility gap with the calculated ones which were obtained by using genetic algorithm. The good agreement between the calculated and experimental results across the entire liquidus is valid evidence in support of the model.

  8. Calculated Pressure Induced BCC-FCC Phase Transitions in Alkali Metals

    OpenAIRE

    DAĞISTANLI, Hamdi; MUTLU, R. Haluk

    2008-01-01

    The partial occupation numbers and density of states (DOS), and the total DOS at the Fermi level are calculated as a function of reduced atomic volume for bcc and fcc alkali metals employing the linear-muffin-tin-orbital (LMTO) method. By means of the abrupt changes obtained in the partial and total DOS values at the Fermi level, good agreement with regard to experiment were found in predicting the bcc-fcc transition volumes of the alkali metals.

  9. Development of processes for the production of solar grade silicon from halides and alkali metals, phase 1 and phase 2

    Science.gov (United States)

    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.

  10. Alkali metal and alkali earth metal gadolinium halide scintillators

    Energy Technology Data Exchange (ETDEWEB)

    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.

  11. METALLIC PHASE AND INSULATING CHARACTER OF ALKALI-EARTH METAL DOPED C60

    Institute of Scientific and Technical Information of China (English)

    曹阳; 陈良进; 陈波; 冯建文; 陈文建

    1995-01-01

    The three dimensional EHMO crystal orbital calculations for crystalline Ba6 C60,Ca3 C60 and Ca5 C60 are reported.The ground state of partially doped Ca3 C60 is found to be insulating with an indrect energy gap of 0.5eV.In contrast,the Ca5 C60 forms a metallic conducting phase with a set of three half-filled bands crossing the Fermi level which is Found to locate close to a peak of the density of state. The character of crystal orbitals near the Fermilevel for both Ca3 C60 and Ca5 C60 is completely carbon-like.In both cases the Ca3 atoms are almost fully ionized and C60 molecules form a stable negative charge state with six to ten additional electrons.The conductivity of Ba6 C60 is resuted from the incomplete charge tranfer.The valance charge of every Ba ion is about 0.33.The total charge tranfer of six Ba atoms is almost the same as that of five Ca atoms.

  12. Process for recovering alkali metals and sulfur from alkali metal sulfides and polysulfides

    Energy Technology Data Exchange (ETDEWEB)

    Gordon, John Howard; Alvare, Javier

    2016-10-25

    Alkali metals and sulfur may be recovered from alkali monosulfide and polysulfides in an electrolytic process that utilizes an electrolytic cell having an alkali ion conductive membrane. An anolyte solution includes an alkali monosulfide, an alkali polysulfide, or a mixture thereof and a solvent that dissolves elemental sulfur. A catholyte includes molten alkali metal. Applying an electric current oxidizes sulfide and polysulfide in the anolyte compartment, causes alkali metal ions to pass through the alkali ion conductive membrane to the catholyte compartment, and reduces the alkali metal ions in the catholyte compartment. Liquid sulfur separates from the anolyte solution and may be recovered. The electrolytic cell is operated at a temperature where the formed alkali metal and sulfur are molten.

  13. Phase diagram and thermodynamic calculations of alkali and alkaline earth metal zirconates

    Energy Technology Data Exchange (ETDEWEB)

    Dash, S. [Bhabha Atomic Res. Centre, Bombay (India). Fuel Chem. Div.; Sood, D.D. [Bhabha Atomic Res. Centre, Bombay (India). Fuel Chem. Div.; Prasad, R. [Bhabha Atomic Res. Centre, Bombay (India). Fuel Chem. Div.

    1996-02-01

    The ternary phase diagrams and partial pressures of various gaseous species over the equilibrium phase fields have been calculated for the M-Zr-O (M=Li, Na, K, Rb, Cs, Sr and Ba) systems by using the SOLGASMIX-PV program, which computes equilibrium composition by direct minimization of the Gibbs energy of a system. The available experimental Gibbs energy data reported in the literature for binary and ternary compounds were used for these calculations. Where no data exist, values were estimated. These ternary phase diagrams are being reported for the first time, except for the lithium system. (orig.).

  14. Phase diagram and thermodynamic calculations of alkali and alkaline earth metal zirconates

    Science.gov (United States)

    Dash, Smruti; Sood, D. D.; Prasad, R.

    1996-02-01

    The ternary phase diagrams and partial pressures of various gaseous species over the equilibrium phase fields have been calculated for the MZrO (M = Li, Na, K, Rb, Cs, Sr and Ba) systems by using the SOLGASMIX-PV program, which computes equilibrium composition by direct minimization of the Gibbs energy of a system. The available experimental Gibbs energy data reported in the literature for binary and ternary compounds were used for these calculations. Where no data exist, values were estimated. These ternary phase diagrams are being reported for the first time, except for the lithium system.

  15. Generation and characterization of alkali metal clusters in Y-FAU zeolites. An ESR and MAS NMR spectroscopic study

    Science.gov (United States)

    Hannus, István; Béres, Attila; Nagy, János B.; Halász, János; Kiricsi, Imre

    1997-06-01

    Charged and neutral metal clusters of various compositions and sizes can be prepared by controlling the alkali metal content by the decomposition of alkali azides and the composition of the host zeolite by ion-exchange. ESR signals show that electron transfer from alkali metal atoms to alkali metal cations does occur, but in a direction opposite to that predicted by the gas-phase thermochemistry. Alkali metal clusters proved to be very active basic catalytic centers.

  16. Nanosized alkali-metal-doped ethoxotitanate clusters.

    Science.gov (United States)

    Chen, Yang; Trzop, Elzbieta; Makal, Anna; Sokolow, Jesse D; Coppens, Philip

    2013-05-06

    The synthesis and crystallographic characterization of alkali-metal-doped ethoxotitanate clusters with 28 and 29 Ti atoms as well as a new dopant-free Ti28 cluster are presented. The light-metal-doped polyoxotitanate clusters in which the alkali-metal atom is the critical structure-determining component are the largest synthesized so far. Calculations show that doping with light alkali atoms narrows the band gap compared with the nondoped crystals but does not introduce additional energy levels within the band gap.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  18. Crystal Structure and Topological Aspects of the High-Temperature Phases of the Alkali-metal Oxalates M-2 C2O4(M= K,Rb, Cs)

    Energy Technology Data Exchange (ETDEWEB)

    Dinnebier,R.; Vensky, S.; Jensen, M.; Hanson, J.

    2005-01-01

    The high-temperature phases of the alkali-metal oxalates M{sub 2}[C{sub 2}O{sub 4}] (M=K, Rb, Cs), and their decomposition products M{sub 2}[CO{sub 3}] (M=K, Rb, Cs), were investigated by fast, angle-dispersive X-ray powder diffraction with an image-plate detector, and also by simultaneous differential thermal analysis (DTA)/thermogravimetric analysis (TGA)/mass spectrometry (MS) and differential scanning calorimetry (DSC) techniques. The following phases, in order of decreasing temperature, were observed and crystallographically characterized (an asterisk denotes a previously unknown modification): *{alpha}-K{sub 2}[C{sub 2}O{sub 4}], *{alpha}-Rb{sub 2}[C{sub 2}O{sub 4}], *{alpha}-Cs{sub 2}[C{sub 2}O{sub 4}], {alpha}-K{sub 2}[CO{sub 3}], *{alpha}-Rb{sub 2}[CO{sub 3}], and *{alpha}-Cs{sub 2}[CO{sub 3}] in space group P6{sub 3}/mmc; *{beta}-Rb{sub 2}[C{sub 2}O{sub 4}], *{beta}-Cs{sub 2}[C{sub 2}O{sub 4}], *{beta}-Rb{sub 2}[CO{sub 3}], and *{beta}-Cs{sub 2}[CO{sub 3}] in Pnma; {gamma}-Rb{sub 2}[C{sub 2}O{sub 4}], {gamma}-Cs[C{sub 2}O{sub 4}], {gamma}-Rb{sub 2}[CO{sub 3}], and {gamma}-Cs{sub 2}[CO{sub 3}] in P2{sub 1}/c; and {delta}-K{sub 2}[C{sub 2}O{sub 4}] and {delta}-Rb{sub 2}[C{sub 2}O{sub 4}] in Pbam. With respect to the centers of gravity of the oxalate and carbonate anions, respectively, the crystal structures of all known alkali-metal oxalates and carbonates belong to the AlB{sub 2} family, and adopt either the AlB{sub 2} or the Ni{sub 2}In arrangement depending on the size of the cation and the temperature. Despite the different sizes and constitutions of the carbonate and oxalate anions, the high-temperature phases of the alkali-metal carbonates M{sub 2}[CO{sub 3}] (M=K, Rb, Cs), exhibit the same sequence of basic structures as the corresponding alkali-metal oxalates. The topological aspects and order-disorder phenomena at elevated temperature are discussed.

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

    Science.gov (United States)

    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.

  20. Removal of Retired Alkali Metal Test Systems

    Energy Technology Data Exchange (ETDEWEB)

    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.

  1. Vibrations of alkali metal overlayers on metal surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Rusina, G G; Eremeev, S V; Borisova, S D [Institute of Strength Physics and Materials Science SB RAS, 634021, Tomsk (Russian Federation); Echenique, P M; Chulkov, E V [Donostia International Physics Center (DIPC), 20018 San Sebastian/Donostia, Basque Country (Spain); Benedek, G [Dipartimento di Scienza dei Materiali, Universita di Milano-Bicocca, Via Cozzi 53, 20125 Milano (Italy)], E-mail: rusina@ispms.tsc.ru

    2008-06-04

    We review the current progress in the understanding of vibrations of alkalis adsorbed on metal surfaces. The analysis of alkali vibrations was made on the basis of available theoretical and experimental results. We also include in this discussion our recent calculations of vibrations in K/Pt(111) and Li(Na)/Cu(001) systems. The dependence of alkali adlayer localized modes on atomic mass, adsorption position and coverage as well as the dependence of vertical vibration frequency on the substrate orientation is discussed. The square root of atomic mass dependence of the vertical vibration energy has been confirmed by using computational data for alkalis on the Al(111) and Cu(001) substrates. We have confirmed that in a wide range of submonolayer coverages the stretch mode energy remains nearly constant while the energy of in-plane polarized modes increases with the increase of alkali coverage. It was shown that the spectrum of both stretch and in-plane vibrations can be very sensitive to the adsorption position of alkali atoms and substrate orientation.

  2. Vibrations of alkali metal overlayers on metal surfaces

    Science.gov (United States)

    Rusina, G. G.; Eremeev, S. V.; Echenique, P. M.; Benedek, G.; Borisova, S. D.; Chulkov, E. V.

    2008-06-01

    We review the current progress in the understanding of vibrations of alkalis adsorbed on metal surfaces. The analysis of alkali vibrations was made on the basis of available theoretical and experimental results. We also include in this discussion our recent calculations of vibrations in K/Pt(111) and Li(Na)/Cu(001) systems. The dependence of alkali adlayer localized modes on atomic mass, adsorption position and coverage as well as the dependence of vertical vibration frequency on the substrate orientation is discussed. The square root of atomic mass dependence of the vertical vibration energy has been confirmed by using computational data for alkalis on the Al(111) and Cu(001) substrates. We have confirmed that in a wide range of submonolayer coverages the stretch mode energy remains nearly constant while the energy of in-plane polarized modes increases with the increase of alkali coverage. It was shown that the spectrum of both stretch and in-plane vibrations can be very sensitive to the adsorption position of alkali atoms and substrate orientation.

  3. High-Order Dispersion Coefficients for Alkali-metal Atoms

    Institute of Scientific and Technical Information of China (English)

    KANG Shuai; DING Chi-Kun; CHEN Chang-Yong; WU Xue-Qing

    2013-01-01

    High-order dispersion coefficients C9,C11,C12,and C13 for the ground-state alkali-metals were calculated by combining the l-dependent model potential of alkali-metal atoms and linear variation method based on B-spline basis functions.The results were compared.

  4. Alkali Metal-incorporated Mesoporous Smectites:Crystallinity and Textural Properties

    Institute of Scientific and Technical Information of China (English)

    HE Yan-feng; Shinichiro Fujita; Nobuhiro Iwasa; Bhalchandra M. Bhanage; Masahiko Arai

    2003-01-01

    A series of mesoporous smectite-like materials incorporated with alkali metals such as Li, Na, K and Cs has been synthesized with the hydrothermal method. The crystalline and the pore structures of the materials synthesized significantly change with the introduction of alkali metals. The addition of Li gives highly ordered layer phases, while the incorporation of Cs yields much less crystalline structures. Although Na or K has little effect on the crystalline structure, they modify the pore structure.

  5. Superconductivity in alkali-metal-doped picene.

    Science.gov (United States)

    Mitsuhashi, Ryoji; Suzuki, Yuta; Yamanari, Yusuke; Mitamura, Hiroki; Kambe, Takashi; Ikeda, Naoshi; Okamoto, Hideki; Fujiwara, Akihiko; Yamaji, Minoru; Kawasaki, Naoko; Maniwa, Yutaka; Kubozono, Yoshihiro

    2010-03-04

    Efforts to identify and develop new superconducting materials continue apace, motivated by both fundamental science and the prospects for application. For example, several new superconducting material systems have been developed in the recent past, including calcium-intercalated graphite compounds, boron-doped diamond and-most prominently-iron arsenides such as LaO(1-x)F(x)FeAs (ref. 3). In the case of organic superconductors, however, no new material system with a high superconducting transition temperature (T(c)) has been discovered in the past decade. Here we report that intercalating an alkali metal into picene, a wide-bandgap semiconducting solid hydrocarbon, produces metallic behaviour and superconductivity. Solid potassium-intercalated picene (K(x)picene) shows T(c) values of 7 K and 18 K, depending on the metal content. The drop of magnetization in K(x)picene solids at the transition temperature is sharp (<2 K), similar to the behaviour of Ca-intercalated graphite. The T(c) of 18 K is comparable to that of K-intercalated C(60) (ref. 4). This discovery of superconductivity in K(x)picene shows that organic hydrocarbons are promising candidates for improved T(c) values.

  6. Controlled in-situ dissolution of an alkali metal

    Energy Technology Data Exchange (ETDEWEB)

    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.

  7. Estimating the hydration enthalpies of neutral alkali metal atoms.

    Science.gov (United States)

    Stace, A J

    2006-10-26

    Using existing data on the ionization energies of alkali metal atoms in small clusters of water, a thermodynamic cycle is proposed from which the hydration enthalpies of the neutral metal atoms can be estimated. Where comparisons are possible, the results are in reasonable agreement with those obtained using both experimental and ab initio methods. Application of the thermodynamic cycle to neutral alkali metal atoms solvated in ammonia yields solvation enthalpies that are significantly lower than those obtained for water.

  8. Directed reflectivity, long life AMTEC condenser (DRC). Final report of Phase II SBIR program[Alkali Metal ThermoElectric Converter

    Energy Technology Data Exchange (ETDEWEB)

    Hunt, Thomas K.

    2001-09-10

    The Alkali Metal Thermal to Electric Converter (AMTEC) is a static energy conversion device that operates at high thermal to electric conversion efficiencies that are essentially independent of size, have reached 19% and are expected to reach 25% to 30% in 1997. AMTEC systems have been chosen by NASA and DOE for spacecraft applications and have considerable promise for a wide variety of terrestrial applications. Reduction of parasitic heat losses in AMTEC systems related to radiative heat transfer from the hot side to the condenser can make a substantial contribution to system efficiency. Through design, analysis and the fabrication and testing of cells and systems, the proposed program to develop a Directed Reflectivity Condenser (DRC) has investigated the feasibility of an improved AMTEC condenser component. Phase 1 work showed the potential for adding from 4% to 7% to overall system efficiency for identical operating conditions using the concept. A detailed thermal analysis of several DRC capped cell designs was carried out and some of the conditions under which a DRC, used as the condenser at an end cap of a cylindrical converter, can reduce thermal radiation related losses were determined. A model experimental converter was built and tested to compare DRC and planar condenser surfaces. The results of both analysis and experiment indicate that for moderate aspect ratios of a cylindrical, end condensed converter, the DRC can reduce overall thermal losses by up to 4%. The initial effort in Phase 2 extended the analysis to a novel 150 watt radial AMTEC cell design. This analysis indicated that for the effective aspect ratio of this new converter design, the system performance at the 100+ watt level was not significantly improved by use of a DRC type condenser surface. Further analyses however showed that for cylindrical, end-condensed converters, optimized for use with internal radiation shields, the use of DRC surfaces on the side walls of the converter could be

  9. Alkali cation specific adsorption onto fcc(111) transition metal electrodes.

    Science.gov (United States)

    Mills, J N; McCrum, I T; Janik, M J

    2014-07-21

    The presence of alkali cations in electrolyte solutions is known to impact the rate of electrocatalytic reactions, though the mechanism of such impact is not conclusively determined. We use density functional theory (DFT) to examine the specific adsorption of alkali cations to fcc(111) electrode surfaces, as specific adsorption may block catalyst sites or otherwise impact surface catalytic chemistry. Solvation of the cation-metal surface structure was investigated using explicit water models. Computed equilibrium potentials for alkali cation adsorption suggest that alkali and alkaline earth cations will specifically adsorb onto Pt(111) and Pd(111) surfaces in the potential range of hydrogen oxidation and hydrogen evolution catalysis in alkaline solutions.

  10. Hall Determination of Atomic Radii of Alkali Metals

    Science.gov (United States)

    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.)

  11. Bioinorganic Chemistry of the Alkali Metal Ions.

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Murugan, A., E-mail: rrpalanichamy@gmail.com; Rajeswarapalanichamy, R., E-mail: rrpalanichamy@gmail.com; Santhosh, M., E-mail: rrpalanichamy@gmail.com; Sudhapriyanga, G., E-mail: rrpalanichamy@gmail.com [Department of Physics, N.M.S.S.V.N College, Madurai, Tamilnadu-625019 (India); Kanagaprabha, S. [Department of Physics, Kamaraj College, Tuticorin, Tamil Nadu-628003 (India)

    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.

  13. Crystal structures and topological aspects of the high-temperature phases and decomposition products of the alkali-metal oxalates M2[C2O4] (M=K, Rb, Cs).

    Science.gov (United States)

    Dinnebier, Robert E; Vensky, Sascha; Jansen, Martin; Hanson, Jonathan C

    2005-02-04

    The high-temperature phases of the alkali-metal oxalates M2[C2O4] (M = K, Rb, Cs), and their decomposition products M2[CO3] (M = K, Rb, Cs), were investigated by fast, angle-dispersive X-ray powder diffraction with an image-plate detector, and also by simultaneous differential thermal analysis (DTA)/thermogravimetric analysis (TGA)/mass spectrometry (MS) and differential scanning calorimetry (DSC) techniques. The following phases, in order of decreasing temperature, were observed and crystallographically characterized (an asterisk denotes a previously unknown modification): *alpha-K2[C2O4], *alpha-Rb2[C2O4], *alpha-Cs2[C2O4], alpha-K2[CO3], *alpha-Rb2[CO3], and *alpha-Cs2[CO3] in space group P6(3)/mmc; *beta-Rb2[C2O4], *beta-Cs2[C2O4], *beta-Rb2[CO3], and *beta-Cs2[CO3] in Pnma; gamma-Rb2[C2O4], gamma-Cs[C2O4], gamma-Rb2[CO3], and gamma-Cs2[CO3] in P2(1)/c; and delta-K2[C2O4] and delta-Rb2[C2O4] in Pbam. With respect to the centers of gravity of the oxalate and carbonate anions, respectively, the crystal structures of all known alkali-metal oxalates and carbonates belong to the AlB2 family, and adopt either the AlB2 or the Ni2In arrangement depending on the size of the cation and the temperature. Despite the different sizes and constitutions of the carbonate and oxalate anions, the high-temperature phases of the alkali-metal carbonates M2[CO3] (M = K, Rb, Cs), exhibit the same sequence of basic structures as the corresponding alkali-metal oxalates. The topological aspects and order-disorder phenomena at elevated temperature are discussed.

  14. Hydrogen storage over alkali metal hydride and alkali metal hydroxide composites

    Institute of Scientific and Technical Information of China (English)

    Pei Yu; Yong Shen Chua; Hujun Cao; Zhitao Xiong; Guotao Wu; Ping Chen

    2014-01-01

    Alkali metal hydroxide and hydride composite systems contain both protic (H bonded with O) and hydridic hydrogen. The interaction of these two types of hydrides produces hydrogen. The enthalpy of dehydrogenation increased with the increase of atomic number of alkali metals, i.e.,-23 kJ/molH2 for LiOH-LiH, 55.34 kJ/molH2 for NaOH-NaH and 222 kJ/molH2 for KOH-KH. These thermodynamic calculation results were consistent with our experimental results. H2 was released from LiOH-LiH system during ball milling. The dehydrogenation temperature of NaOH-NaH system was about 150◦C; whereas KOH and KH did not interact with each other during the heating process. Instead, KH decomposed by itself. In these three systems, NaOH-NaH was the only reversible hydrogen storage system, the enthalpy of dehydrogenation was about 55.65 kJ/molH2 , and the corresponding entropy was ca. 101.23 J/(molH2 ·K), so the temperature for releasing 1.0 bar H2 was as high as 518◦C, showing unfavorable thermodynamic properties. The activation energy for hydrogen desorption of NaOH-NaH was found to be 57.87 kJ/mol, showing good kinetic properties.

  15. Neuropsychiatric manifestations of alkali metal deficiency and excess

    Energy Technology Data Exchange (ETDEWEB)

    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.

  16. Cations in a Molecular Funnel: Vibrational Spectroscopy of Isolated Cyclodextrin Complexes with Alkali Metals

    NARCIS (Netherlands)

    Gamez, F.; Hurtado, P.; Hortal, A. R.; Martinez-Haya, B.; G. Berden,; Oomens, J.

    2013-01-01

    The benchmark inclusion complexes formed by -cyclodextrin (CD) with alkali-metal cations are investigated under isolated conditions in the gas phase. The relative CD-M+ (M=Li+, Na+, K+, Cs+) binding affinities and the structure of the complexes are determined from a combination of mass spectrometry,

  17. Hydrogen Release Studies of Alkali Metal Amidoboranes

    Energy Technology Data Exchange (ETDEWEB)

    Luedtke, Avery T.; Autrey, Thomas

    2010-04-19

    A series of metal amido boranes LiNH2BH3 (LAB), NaNH2BH3 (SAB), LiNH(Me)BH3 (LMAB), NaNH(Me)BH3 (SMAB), KNH(Me)BH3 (PMAB), and KNH(tBu)BH3 (PBAB) were synthesized, by solution phase methods, and the thermal release of H2 in the solid state was studied. Based on the observed trends in reaction rates of H > Me > tBu and the kinetic isotope effect, the mechanism of hydrogen release from MAB compounds was found to proceed through a bimolecular mechanism involving the intermediacy of a MH (M = Li, Na, or K). The mechanism of hydrogen release from metal amidoboranes, a metal ion assisted hydride transfer, is very different than the mechanism of hydrogen release from the parent compound ammonia borane (AB). The non-volatile products formed from MAB’s are significantly different than the products formed after hydrogen release from AB. The boron containing resulting from the release of one equivalent of hydrogen from the metal amidoboranes were characterized by MAS 11B NMR spectroscopy and found to contain both BH3 and sp2 hybridized BH groups, consistent with a general structural feature MN(R)=BHN(R)MBH3. This work was funded by the U.S. Department of Energy Office of Energy Efficiency and Renewable Energy as part of the Chemical Hydrogen Storage CoE at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the U.S. DOE by Battelle. MAS NMR studies were performed using EMSL, a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research located at PNNL.

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

    Science.gov (United States)

    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.

  19. Thermodynamic study of alkali metals release in pressurised fluidised-bed combustion and gasification of peat

    Energy Technology Data Exchange (ETDEWEB)

    Mojtahedi, W.; Backman, R.; Korhonen, M.

    1988-01-01

    A combined-cycle power generation system incorporating pressurised fluidised-bed combustion (PFBC) or gasification is considered a promising approach for electricity generation using solid fuels such as peat. In these systems, the high-pressure hot flue gas is expanded in a gas turbine. Peat contains sodium and potassium which are released in combustion and gasification. These are corrosive elements that can cause severe damage to the turbine blades if not suppressed. Multicomponent, multiphase equilibrium calculations were carried out for atmospheric and pressurised fluidised-bed operating conditions to determine the relative distribution of the two metals (Na and K) in the gas and condensed phases. Dependence of the alkali volatilisation on the operating temperature, pressure, the chlorine-content and the total alkali-content of the feedstock was studied. The results show that the alkali release in the vapour-phase could be much higher than acceptable to a gas turbine, particularly under gasification conditions. Hence the necessity to remove the volatilised alkali-metal compounds is more acute in gasification than in combustion. Both sodium and potassium are present as chlorides and to a lesser extent as hydroxides in the gas phase in both modes of operation (i.e. combustion and gasification). However, whereas under combustion conditions both metals seem to condense as sulphates (Na/sub 2/SO4 and K/sub 2/SO4), in gasification, chlorides and carbonates dominate in the condensed phase. The alkali-metals volatilisation shows strong dependence on the operating pressure of the system as well as on the chlorine-content of the feedstock. It decreases markedly with the former but increases sharply with the latter.

  20. Density functional study of ferromagnetism in alkali metal thin films

    Indian Academy of Sciences (India)

    Prasenjit Sen

    2010-04-01

    Electronic and magnetic structures of (1 0 0) films of K and Cs, having thicknesses of one to seven layers, are calculated within the plane-wave projector augmented wave (PAW) formalism of the density functional theory (DFT), using both local spin density approximation (LSDA) and the PW91 generalized gradient approximation (GGA). Only a six-layer Cs film is found to have a ferromagnetic (FM) state which is degenerate with a paramagnetic (PM) state within the accuracy of these calculations. These results are compared with those obtained from calculations on a finite-thickness uniform jellium model (UJM), and it is argued that within LSDA or GGA, alkali metal thin films cannot be claimed to have an FM ground state. Relevance of these results to the experiments on transition metal-doped alkali metal thin films and bulk hosts are also discussed.

  1. Modified PVA-CA blend ultrafiltration membrane by alkali metal chloride

    Institute of Scientific and Technical Information of China (English)

    张启修; 邱运仁

    2003-01-01

    The modified PVA-CA blend ultrafiltration membranes were prepared by phase inversion from the casting solutions consisting of polyvinyl alcohol(PVA), cellulose acetate(CA), acetic acid, alkali metal chloride and water. The effects of different concentration of alkali metal chloride on the properties of membranes were investigated. The results show that when the mass fraction of the salt in the casting solution is not greater than 1%, the property of rejection of the alkali metal salt modified ultrafiltration PVA-CA blend membrane has little change compared with that of the unmodified PVA-CA blend membrane, but the permeation flux is much greater than that of the unmodified membrane under the same operation condition. When the mass fraction of the salt is greater than 1.5%, the permeate flux increases much greater than that of the unmodified membrane, but the property of rejection of the modified ultrafiltration membrane decreases greatly. The results also show that the contact angle of the salt modified PVA-CA blend UF membrane decreases but the swelling in water increases with the increment of the mass fraction of alkali metal salts. Furthermore, the NaCl modified PVA-CA blend membrane has a slightly lower swelling and a little smaller contact angle of water than the KCl modified PVA-CA blend membrane does when the mass fraction of salts is the same.

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

    Energy Technology Data Exchange (ETDEWEB)

    Henning, Robert [Iowa State Univ., Ames, IA (United States)

    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 Cs8Ga11. The geometry of the Ga117- unit is not deltahedral but can be described as a penta-capped trigonal prism. The reduction of the charge from a closo-Ga1113- to Ga117- 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 Na10Ga10Ni 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 K2Ga3 Octahedra are connected through four waist atoms to form a layered structure with the potassium atoms sitting between the layers. Na30.5Ga60-xAgx is nonstoichiometric and needs only a small amount of silver to form (x ~ 2-6). The structure is composed of three different clusters which are interconnected to form a three-dimensional structure. The RbGa3-xAux system is also nonstoichiometric with a three-dimensional structure composed of Ga8 dodecahedra and four-bonded gallium atoms. Unlike Na30.5Ga60-xAgx, the RbGa3 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

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

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Fluorinated carboxylic acid alkali... 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. Chemical compatibility of structural materials in alkali metals

    Energy Technology Data Exchange (ETDEWEB)

    Natesan, K.; Rink, D.L.; Haglund, R. [Argonne National Lab., Chicago, IL (United States)] [and others

    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.

  5. Polarizabilities and hyperpolarizabilities of the alkali metal atoms

    Energy Technology Data Exchange (ETDEWEB)

    Fuentealba, P. (Chile Univ., Santiago (Chile). Departamento de Fisica and Centro de Mecanica Cuantica Aplicada (CMCA)); Reyes, O. (Chile Univ., Santiago (Chile). Dept. de Fisica)

    1993-08-14

    The electric static dipole polarizability [alpha], quadrupole polarizability C, dipole-quadrupole polarizability B, and the second dipole hyperpolarizability [gamma] have been calculated for the alkali metal atoms in the ground state. The results are based on a pseudopotential which is able to incorporate the very important core-valence correlation effect through a core polarization potential, and, in an empirical way, the main relativistic effects. The calculated properties compare very well with more elaborated calculations for the Li atom, excepting the second hyperpolarizability [gamma]. For the other atoms, there is neither theoretical nor experimental information about most of the higher polarizabilities. Hence, the results of this paper should be seen as a first attempt to give a complete account of the series expansion of the interaction energy of an alkali metal atom and a static electric field. (author).

  6. Composition and thermodynamic properties of dense alkali metal plasmas

    Energy Technology Data Exchange (ETDEWEB)

    Gabdullin, M.T. [NNLOT, al-Farabi Kazakh National University, 71 al-Farabi Str., Almaty 050035 (Kazakhstan); Ramazanov, T.S.; Dzhumagulova, K.N. [IETP, al-Farabi Kazakh National University, 71 al-Farabi Str., Almaty 050035 (Kazakhstan)

    2012-04-15

    In this work composition and thermodynamic properties of dense alkali metal plasmas (Li, Na) were investigated. Composition was derived by solving the Saha equations with corrections due to nonideality. The lowering of the ionization potentials was calculated on the basis of pseudopotentials by taking screening and quantum effects into account (copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

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

    Science.gov (United States)

    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.

  8. The unexpected properties of alkali metal iron selenide superconductors

    Energy Technology Data Exchange (ETDEWEB)

    Dagotto, Elbio R [ORNL

    2013-01-01

    The iron-based superconductors that contain FeAs layers as the fundamental building block in the crystal structures have been rationalized in the past using ideas based on the Fermi surface nesting of hole and electron pockets when in the presence of weak Hubbard U interactions. This approach seemed appropriate considering the small values of the magnetic moments in the parent compounds and the clear evidence based on photoemission experiments of the required electron and hole pockets. However, recent results in the context of alkali metal iron selenides, with generic chemical composition AxFe2ySe2 (A alkali metal element), have challenged those previous ideas since at particular compositions y the low-temperature ground states are insulating and display antiferromagnetic order with large iron magnetic moments. Moreover, angle-resolved photoemission studies have revealed the absence of hole pockets at the Fermi level in these materials. The present status of this exciting area of research, with the potential to alter conceptually our understanding of the ironbased superconductors, is here reviewed, covering both experimental and theoretical investigations. Other recent related developments are also briefly reviewed, such as the study of selenide two-leg ladders and the discovery of superconductivity in a single layer of FeSe. The conceptual issues considered established for the alkali metal iron selenides, as well as several issues that still require further work, are discussed.

  9. Heterometallic aluminates: alkali metals trapped by an aluminium aryloxide claw.

    Science.gov (United States)

    Muñoz, M Teresa; Cuenca, Tomás; Mosquera, Marta E G

    2014-10-14

    A series of heterometallic aluminium-alkali metal species [AlMMe2{2,6-(MeO)2C6H3O}2]n have been isolated for lithium, sodium and potassium. These compounds can be generated by the reaction of [AlMe2{2,6-(MeO)2C6H3O}]2 with the metallated phenol [M{2,6-(MeO)2C6H3O}]n or through the reaction of the mixture of AlMe3 and the appropriate alkali metal alkyl base with two equivalents of 2,6-dimethoxyphenol. In the heterometallic species obtained, the {AlMe2{2,6-(MeO)2C6H3O}2}(-) moiety is observed and could be described as a claw which fixes the alkali ion by the phenoxide oxygen atoms while the methoxy groups help to stabilize their coordination sphere. All compounds have been characterized by NMR spectroscopy and X-ray diffraction methods. Catalytic studies reveal that these compounds are active in ring-opening polymerization of L-lactide.

  10. Alkali metal cation-hexacyclen complexes: effects of alkali metal cation size on the structure and binding energy.

    Science.gov (United States)

    Austin, C A; Rodgers, M T

    2014-07-24

    Threshold collision-induced dissociation (CID) of alkali metal cation-hexacyclen (ha18C6) complexes, M(+)(ha18C6), with xenon is studied using guided ion beam tandem mass spectrometry techniques. The alkali metal cations examined here include: Na(+), K(+), Rb(+), and Cs(+). In all cases, M(+) is the only product observed, corresponding to endothermic loss of the intact ha18C6 ligand. The cross-section thresholds are analyzed to extract zero and 298 K M(+)-ha18C6 bond dissociation energies (BDEs) after properly accounting for the effects of multiple M(+)(ha18C6)-Xe collisions, the kinetic and internal energy distributions of the M(+)(ha18C6) and Xe reactants, and the lifetimes for dissociation of the activated M(+)(ha18C6) complexes. Ab initio and density functional theory calculations are used to determine the structures of ha18C6 and the M(+)(ha18C6) complexes, provide molecular constants necessary for the thermodynamic analysis of the energy-resolved CID data, and theoretical estimates for the M(+)-ha18C6 BDEs. Calculations using a polarizable continuum model are also performed to examine solvent effects on the binding. In the absence of solvent, the M(+)-ha18C6 BDEs decrease as the size of the alkali metal cation increases, consistent with the noncovalent nature of the binding in these complexes. However, in the presence of solvent, the ha18C6 ligand exhibits selectivity for K(+) over the other alkali metal cations. The M(+)(ha18C6) structures and BDEs are compared to those previously reported for the analogous M(+)(18-crown-6) and M(+)(cyclen) complexes to examine the effects of the nature of the donor atom (N versus O) and the number donor atoms (six vs four) on the nature and strength of binding.

  11. Synthesis and Characterization of Novel Ternary and Quaternary Alkali Metal Thiophosphates

    KAUST Repository

    Alahmary, Fatimah S.

    2014-05-01

    The ongoing development of nonlinear optical (NLO) crystals such as coherent mid-IR sources focuses on various classes of materials such as ternary and quaternary metal chalcophosphates. In case of thiophosphates, the connection between PS4-tetrahedral building blocks and metals gives rise to a broad structural variety where approximately one third of all known ternary (A/P/S) and quaternary (A/M/P/S) (A = alkali metal, M = metal) structures are acentric and potential nonlinear optical materials. The molten alkali metal polychalcophosphate fluxes are a well-established method for the synthesis of new ternary and quaternary thiophosphate and selenophosphate compounds. It has been a wide field of study and investigation through the last two decades. Here, the flux method is used for the synthesis of new quaternary phases containing Rb, Ag, P and S. Four new alkali metal thiophosphates, Rb4P2S10, RbAg5(PS4), Rb2AgPS4 and Rb3Ag9(PS4)4, have been synthesized successfully from high purity elements and binary starting materials. The new compounds were characterized by single crystal and powder X-ray diffraction, scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), ultraviolet-visible (UV-VIS), Raman spectroscopy, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). These compounds show interesting structural variety and physical properties. The crystal structures feature 3D anionic framework built up of PS4 tetrahedral units and charge balanced by Ag and alkali metal cations. All prepared compounds are semiconductors with band gap between 2.3 eV to 2.6 eV and most of them are thermally stable up to 600ºC.

  12. Formation of alkali-metal nanoparticles in alkali-silicate glasses under electron irradiation and thermal processing

    Science.gov (United States)

    Bochkareva, E. S.; Sidorov, A. I.; Ignat'ev, A. I.; Nikonorov, N. V.; Podsvirov, O. A.

    2017-02-01

    Experiments and numerical simulation show that the irradiation of alkali-containing glasses using electrons at an energy of 35 keV and the subsequent thermal processing at a temperature above the vitrification point lead to the formation of spherical metal (lithium, sodium, and potassium) nanoparticles with oxide sheaths that exhibit plasmon resonances in the visible spectral range. Glasses containing two alkali metals exhibit mutual effect of metals on the formation of nanoparticles with two compositions due to the difference of ion radii and mobilities of metal ions.

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

    Science.gov (United States)

    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. Structural and Dynamical Trends in Alkali-Metal Silanides Characterized by Neutron-Scattering Methods

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Wan Si; Dimitrievska, Mirjana; Chotard, Jean-Noel; Zhou, Wei; Janot, Raphael; Skripov, Alexander V.; Udovic, Terrence J.

    2016-09-29

    Structural, vibrational, and dynamical properties of the mono- and mixed-alkali silanides (MSiH3, where M = K, Rb, Cs, K0.5Rb0.5, K0.5Cs0.5, and Rb0.5Cs0.5) were investigated by various neutron experiments, including neutron powder diffraction (NPD), neutron vibrational spectroscopy (NVS), neutron-scattering fixed-window scans (FWSs), and quasielastic neutron scattering (QENS) measurements. Structural characterization showed that the mixed compounds exhibit disordered (..alpha..) and ordered (..beta..) phases for temperatures above and below about 200-250 K, respectively, in agreement with their monoalkali correspondents. Vibrational and dynamical properties are strongly influenced by the cation environment; in particular, there is a red shift in the band energies of the librational and bending modes with increasing lattice size as a result of changes in the bond lengths and force constants. Additionally, slightly broader spectral features are observed in the case of the mixed compounds, indicating the presence of structural disorder caused by the random distribution of the alkali-metal cations within the lattice. FWS measurements upon heating showed that there is a large increase in reorientational mobility as the systems go through the order-disorder (..beta..-..alpha..) phase transition, and measurements upon cooling of the ..alpha..-phase revealed the known strong hysteresis for reversion back to the ..beta..-phase. Interestingly, at a given temperature, among the different alkali silanide compounds, the relative reorientational mobilities of the SiH3- anions in the ..alpha..- and ..beta..-phases tended to decrease and increase, respectively, with increasing alkali-metal mass. This dynamical result might provide some insights concerning the enthalpy-entropy compensation effect previously observed for these potentially promising hydrogen storage materials.

  15. Periodic DFT approaches to crystalline alkali metal azides

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The energy bands, electronic structures andrelationship between structures and properties of the crys-talline alkali metal azides, LiN3, α-NaN3 and KN3, are investigated at the DFT-B3LYP level. The crystalline bulks arepredicted to be insulator, speculated from their band gaps ofca. 0.23-0.25 a.u. and from their level frontier bands. Theatomic overlaps and electron densities show that the metalsand the azides are combined by ionic bonds. The crystal lat-tice energies, being corrected for the basis set superpositionerrors, are -852.30, -771.45 and - 614.78 kJ @ mol-1 for LiN3,α-NaN3 and KN3 respectively. These values are similar tothose by Gray's approximate method. The frontier crystalorbital mainly consists of the atomic orbital of the terminalnitrogen of azides. The contribution of the metallic orbital tothe LUMO is very small. The electron transition from theHOMO to the LUMO is difficult to occur. Hence all the al-kali metal azides are expected to be insensitive explosives,according to the "principle of easiest electron transition".

  16. Integrated oil production and upgrading using molten alkali metal

    Energy Technology Data Exchange (ETDEWEB)

    Gordon, John Howard

    2016-10-04

    A method that combines the oil retorting process (or other process needed to obtain/extract heavy oil or bitumen) with the process for upgrading these materials using sodium or other alkali metals. Specifically, the shale gas or other gases that are obtained from the retorting/extraction process may be introduced into the upgrading reactor and used to upgrade the oil feedstock. Also, the solid materials obtained from the reactor may be used as a fuel source, thereby providing the heat necessary for the retorting/extraction process. Other forms of integration are also disclosed.

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

    Science.gov (United States)

    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.

  18. Alkali and heavy metal emissions of the PCFB-process; Alkali- ja raskasmetallipaeaestoet PCFB-prosessista

    Energy Technology Data Exchange (ETDEWEB)

    Kuivalainen, R.; Eriksson, T.; Lehtonen, P. [Foster Wheeler Energia Oy, Karhula (Finland)

    1997-10-01

    Pressurized Circulating Fluidized Bed (PCFB) combustion technology has been developed in Karhula R and D Center since 1986. As part of the development, 10 MW PCFB test facility was built in 1989. The test facility has been used for performance testing with different coal types through the years 1990-1995 in order to gain data for design and commercialization of the high-efficiency low-emission PCFB combustion technology. The main object of the project was to measure vapor phase Na and K concentrations in the PCFB flue gas after hot gas filter and investigate the effects of process conditions and sorbents on alkali release. The measurements were performed using plasma assisted method of TUT Laboratory of Plasma Technology and wet absorption method of VTT Energy. The measurements were carried out during three test campaigns at PCFB Test Facility in Karhula. In autumn 1995 both VTT and TUT methods were used. The measurements of the following test period in spring 1996 were performed by VTT, and during the last test segment in autumn 1996 TUT method was in use. During the last test period, the TUT instrument was used as semi-continuous (3 values/minute) alkali analyzer for part of the time. The measured Na concentrations were below 30 ppb(w) in all measured data points. The results of K were below 10 ppb(w). The accuracies of the both methods are about +50 % at this concentration range. The scatter of the data covers the effects of different process variables on the alkali emission. The measured emissions are at the same order of magnitude as the guideline emission limits estimated by gas turbine manufacturers

  19. Alkali-metalated forms of thiacalix[4]arenes.

    Science.gov (United States)

    Zeller, Jürgen; Radius, Udo

    2006-11-13

    The alkali metal salts [TCALi4] (1), [TCANa4] (2), and [TCALK4] (3) of fully deprotonated p-tert-butyltetrathiacalix[4]arene (H(4)TCA) are readily available from the reactions of thiacalix[4]arene and n-BuLi, NaH, or KH as deprotonating reagents. Crystals of the sodium salts 2 and the potassium salt 3 suitable for X-ray diffraction were obtained in the form of the pyridine solvates [(TCA)2Na8.8py] (2.8py) and [(TCA)2K(8).8py] (3.8py). These molecules are dimers in the solid state but are structurally not related. In addition, the reaction of H(4)TCA and lithium hydroxide afforded the structurally characterized complex [(TCA)Li5(OH).4THF] (4). The molecular structure of 4 as well as the structures of 2.8py and 3.8py reveal a close relationship to the corresponding alkali metal salts of the calix[4]arenes.

  20. Molten salt phase diagram evaluation by pattern recognition:Part Ⅰ Divalent rare earth halide and alkali metal halide binary systems

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    At present CALPHAD (CALculation of PHAse Diagram) technique is not capable of predicting whether there exists intermediate compound, much less predicting the formulae, the number, and the melting congruence of intermediate compounds. To solve this problem, a new approach called the phase diagram evaluation by pattern recognition (PDEPR) was improved. The micro-parameters, such as the radius and the electronegativity of the element, were used as original features and then they were transformed and spanned to the different features in multi-dimensional space.Then a set of classifying functions were obtained to predict the information of intermediate compounds in REX2-AX systems (RE-rare earth element; A-Li, Na, K, Rb, and Cs; X F, Cl, Br, and 1). It is comparatively important for the design of materials.

  1. Hydration number of alkali metal ions determined by insertion in a conducting polymer

    DEFF Research Database (Denmark)

    Skaarup, Steen

    2008-01-01

    . The solvation of alkali metal ions has been discussed for many years without a clear consensus. This work presents a systematic study of the hydration numbers of the 5 alkali metal ions, using the electrochemical insertion of the ions in a conducting polymer (polypyrrole containing the large immobile anion DBS...

  2. Hydride encapsulation by molecular alkali-metal clusters.

    Science.gov (United States)

    Haywood, Joanna; Wheatley, Andrew E H

    2008-07-14

    The sequential treatment of group 12 and 13 Lewis acids with alkali-metal organometallics is well established to yield so-called ''ate' complexes, whereby the Lewis-acid metal undergoes nucleophilic attack to give an anion, at least one group 1 metal acting to counter this charge. However, an alternative, less well recognised, reaction pathway involves the Lewis acid abstracting hydride from the organolithium reagent via a beta-elimination mechanism. It has recently been shown that in the presence of N,N'-bidentate ligands this chemistry can be harnessed to yield a new type of molecular main-group metal cluster in which the abstracted LiH is effectively trapped, with the hydride ion occupying an interstitial site in the cluster core. Discussion focuses on the development of this field, detailing advances in our understanding of the roles of Lewis acid, organolithium, and amine substrates in the syntheses of these compounds. Structure-types are discussed, as are efforts to manipulate cluster geometry and composition as well as hydride-coordination. Embryonic mechanistic studies are reported, as well as attempts to generate hydride-encapsulation clusters under catalytic control.

  3. 3718-F Alkali Metal Treatment and Storage Facility Closure Plan

    Energy Technology Data Exchange (ETDEWEB)

    None

    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.

  4. An alternative picture of alkali-metal-mediated metallation: cleave and capture chemistry.

    Science.gov (United States)

    Mulvey, Robert E

    2013-05-21

    This perspective article takes an alternative look at alkali-metal-mediated chemistry (exchange of a relatively inert C-H bond for a more reactive C-metal bond by a multicomponent reagent usually containing an alkali metal and a less electropositive metal such as magnesium or zinc). It pictures that the cleavage of selected C-H bonds can be accompanied by the capturing of the generated anion by the multi (Lewis acid)-(Lewis base) character of the residue of the bimetallic base. In this way small atoms or molecules (hydrides, oxygen-based anions) as well as sensitive organic anions (of substituted aromatic compounds, ethers or alkenes) can be captured. Cleave and capture reactions which occur in special positions on the organic substrate are also included.

  5. Examination of Solubility Models for the Determination of Transition Metals within Liquid Alkali Metals

    Directory of Open Access Journals (Sweden)

    Jeremy Isler

    2016-06-01

    Full Text Available The experimental solubility of transition metals in liquid alkali metal was compared to the modeled solubility calculated using various equations for solubility. These equations were modeled using the enthalpy calculations of the semi-empirical Miedema model and various entropy calculations. The accuracy of the predicted solubility compared to the experimental data is more dependent on which liquid alkali metal is being examined rather than the transition metal solute examined. For liquid lithium the calculated solubility by the model was generally larger than experimental values, while for liquid cesium the modeling solubility was significantly smaller than the experimental values. For liquid sodium, potassium, and rubidium the experimental solubilities were within the range calculated by this study. Few data approached the predicted temperature dependence of solubility and instead most data exhibited a less pronounced temperature dependence.

  6. Assessment of alkali metal coolants for the ITER blanket

    Science.gov (United States)

    Natesan, K.; Reed, C. B.; Mattas, R. F.

    1994-06-01

    The blanket system is one of the most important components of a fusion reactor because it has a major impact on both the economics and safety of fusion energy. The primary functions of the blanket in a deuterium/tritium-fueled fusion reactor are to convert the fusion energy into sensible heat and to breed tritium for the fuel cycle. The blanket comparison and selection study, conducted earlier, described the overall comparative performance of different blanket concepts, including liquid metal, molten salt, water, and helium. This paper will discuss the ITER requirements for a self-cooled blanket concept with liquid lithium and for indirectly cooled concepts that use other alkali metals such as NaK. The paper addresses the thermodynamics of interactions between the liquid metals (e.g., lithium and NaK) and structural materials (e.g., V-base alloys), together with associated corrosion/compatibility issues. Available experimental data are used to assess the long-term performance of the first wall in a liquid metal environment. Other key issues include development of electrical insulator coatings on the first-wall structural material to MHD pressure drop, and tritium permeation/inventory in self-cooled and indirectly cooled concepts. Acceptable types of coatings (based on their chemical compatibility and physical properties) are identified, and surface-modification avenues to achieve these coatings on the first wall are discussed. The assessment examines the extent of our knowledge on structural materials performance in liquid metals and identifies needed research and development in several of the areas in order to establish performance envelopes for the first wall in a liquid-metal environment.

  7. Thermochemical Ablation Therapy of VX2 Tumor Using a Permeable Oil-Packed Liquid Alkali Metal

    OpenAIRE

    2015-01-01

    Objective Alkali metal appears to be a promising tool in thermochemical ablation, but, it requires additional data on safety is required. The objective of this study was to explore the effectiveness of permeable oil-packed liquid alkali metal in the thermochemical ablation of tumors. Methods Permeable oil-packed sodium–potassium (NaK) was prepared using ultrasonic mixing of different ratios of metal to oil. The thermal effect of the mixture during ablation of muscle tissue ex vivo was evaluat...

  8. Alkali and heavy metal emissions of the PCFB-process; Alkalipaeaestoet PCFB-prosessissa

    Energy Technology Data Exchange (ETDEWEB)

    Kuivalainen, R.; Eriksson, T.; Lehtonen, P. [Foster Wheeler Energia Oy, Karhula (Finland)

    1996-12-01

    Pressurized Circulating Fluidized Bed (PCFB) combustion technology has been developed in Karhula R and D Center since 1986. As a part of the development, 10 MW PCFB Test Facility was built in 1989. The Test Facility has been used for performance testing with different coal types through the years 1990-1995 in order to gain data for design and commercialization of the high-efficiency low-emission PCFB combustion technology. The project Y44 `Alkali and heavy metal emissions of the PCFB-process` was part of national LIEKKI 2 research program. The main object of the project was to measure vapor phase Na and K concentrations in the PCFB flue gas after hot gas filter and investigate the effects of process conditions and sorbents on alkali release. The measurements were performed using plasma assisted method by TUT Laboratory of Plasma Technology and wet absorption method of VTT Energy. The measured Na concentrations were below 30 ppb(w) in all measured data points. The results of K were below 10 ppb(w). The accuracies of the both methods are about + 50 % at this concentration range. The scatter of the data covers the effects of different process variables on the alkali emission. The measured emissions are at the same order of magnitude as the guideline emission limits estimated by gas turbine manufacturers. The measurements and development of the analyses methods are planned to be continued during PCFB test runs in spring 1996 for example within Joule II research program. (author)

  9. Field emission properties of capped carbon nanotubes doped by alkali metals:a theoretical investigation

    Institute of Scientific and Technical Information of China (English)

    Jin Lei; Fu Hong-Gang; Xie Ying; Yu Hai-Tao

    2012-01-01

    The electronic structures and field emission properties of capped CNT55 systems with or without alkali metal atom adsorption were systematically investigated by density functional theory calculation.The results indicate that the adsorption of alkali metal on the center site of a CNT tip is energetically favorable.In addition,the adsorption energies increase with the introduction of the electric field.The excessive negative charges on CNT tips make electron emittance much easier and result in a decrease in work function.Furthermore,the inducing effect by positively charged alkali metal atoms can be reasonably considered as the dominant reason for the improvement in field emission properties.

  10. Alkali-metal-supported bismuth polyhedra-principles and theoretical studies.

    Science.gov (United States)

    Monakhov, Kirill Yu; Linti, Gerald; Wolters, Lando P; Bickelhaupt, F Matthias

    2011-06-20

    We have quantum chemically investigated the structure, stability, and bonding mechanism in highly aggregated alkali-metal salts of bismuthanediide anions [RBi](2-) using relativistic density functional theory (DFT, at ZORA-BP86/TZ2P) in combination with a quantitative energy decomposition analysis (EDA). Our model systems are alkali-metal-supported bismuth polyhedra [(RBi)(n)M(2n-4)](4-) with unique interpenetrating shells of a bismuth polyhedron and an alkali-metal superpolyhedron. Furthermore, we have analyzed the trianionic inclusion complexes [M'@{(RBi)(n)M(2n-4)}](3-) involving an additional endohedral alkali-metal ion M'. The main objective is to assist the further development of synthetic approaches toward this class of compounds. Our analyses led to electron-counting rules relating, for example, the number of bonding orbitals (N(bond)) of the cage molecules [(RBi)(n)M(2n+Q)](Q) to the number of bismuth atoms (n(Bi)), alkali-metal atoms (n(M)), and net charge Q as N(bond) = n(Bi) + n(M) - Q (R = one-electron donor ligand; M = alkali metal; n = 4-12; Q = -4, -6, -8). Finally, on the basis of our findings, we predict the next members in the 5-fold symmetrical row of alkali-metallobismaspheres with a macroicosahedral arrangement.

  11. Structural properties of low-density liquid alkali metals

    Indian Academy of Sciences (India)

    A Akande; G A Adebayo; O Akinlade

    2005-12-01

    The static structure factors of liquid alkali metals have been modelled at temperatures close to their melting points and a few higher temperatures using the reverse Monte Carlo (RMC) method. The positions of 5000 atoms in a box, with full periodicity, were altered until the experimental diffraction data of the structure factor agrees with the associated model structure factor within the errors. The model generated is then analysed. The position of the first peak of the pair distribution function () does not show any significant temperature dependence and the mean bond lengths can be approximated within an interval of 3.6–5.3 Å, 4.5–6.6 Å, 4.8–6.7 Å and 5.1–7.3 Å for Na, K, Rb and Cs respectively. The cosine bond distributions show similar trend with the flattening up of the first peak with increase in temperature. In addition, the coordination numbers of these liquid metals are high due to the presence of non-covalent bonding between them. On the average, we surmise that the coordination number decreases with increase in temperature.

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

    Science.gov (United States)

    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).

  13. A contribution to the surface characterization of alkali metal sulfates

    Energy Technology Data Exchange (ETDEWEB)

    Fantauzzi, Marzia; Rigoldi, Americo; Elsener, Bernhard; Atzei, Davide; Rossi, Antonella, E-mail: rossi@unica.it

    2014-03-01

    Highlights: • Full electronic characterization of alkali metals sulfates by X-ray photoelectron spectroscopy and X-ray induced Auger electron spectroscopy. • Curve-fitting of SKLL signals makes possible to clarify the role of the cation in the series of alkali metal sulfates. • Differences in the binding energies and Auger parameter are discussed in terms of the electronic properties and the polarizability of the cation. • The line intensities are analyzed and a thorough quantitative analysis is presented. - Abstract: The analytical characterization of surfaces of sulfur-bearing samples that present sulfides, polysulfides and/or elemental sulfur as reaction products can be difficult by simply relying on the binding energy of the S2p X-ray photoelectron signals, due to the small chemical shifts. In such cases the Auger parameter concept can be used to distinguish among different chemical states, but this requires a model to curve fit complex Auger SKLL signals in order to resolve the contributions arising from sulfur in different chemical states on the surface. With this scope a detailed X-ray photoelectron spectroscopy (XPS) and X-ray induced Auger electron spectroscopy (XAES) surface analytical study of the group IA sulfates is presented in this paper. Sulfates were chosen as model compounds for curve fitting the X-ray induced SKLL spectra since in these compounds sulfur is present in a unique chemical state. For the first time the multicomponent SKLL spectra are fitted with model functions consisting of an intense {sup 1}D and a low intensity {sup 1}S contribution with constant energy difference of 8 eV. It was found that the kinetic energy of the SK{sub 2,3}L{sub 2,3} ({sup 1}D) line increases from 2105.1 ± 0.1 to 2107.5 ± 0.2 eV whereas the corresponding S2p{sub 3/2} binding energy decreases from 169.5 ± 0.1 eV for Li{sub 2}SO{sub 4} to 167.8 ± 0.1 eV for Cs{sub 2}SO{sub 4}. Shifts to lower binding energy values are observed also for S2p, S2s and O1

  14. Properties of Hydrated Alkali Metals Aimed at the Ion Channel Selectivity

    Institute of Scientific and Technical Information of China (English)

    AN Hai-Long; LIU Yu-Zhi; ZHANG Su-Hua; ZHAN Yong; ZHANG Hai-Lin

    2008-01-01

    The hydration structure properties of different alkali metal ions with eight water molecules and potassium ions with different numbers of water molecules are studied using the mixed density functional theory, B3LYP, with 6-311G basis set. The hydration structures are obtained from structure optimization and the optimum numbers of water molecules in the innermost hydration shell for the alkali metal ions are found. Some useful information about the ion channel selectivity is presented.

  15. Improved hydrogen desorption from lithium hydrazide by alkali metal hydride

    Energy Technology Data Exchange (ETDEWEB)

    Zeng, Liang, E-mail: liangzeng@hiroshima-u.ac.jp [Institute for Advanced Materials Research, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima 739-8530 (Japan); Miyaoka, Hiroki [Institute for Sustainable Sciences and Development, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima 739-8530 (Japan); Ichikawa, Takayuki; Kojima, Yoshitsugu [Institute for Advanced Materials Research, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima 739-8530 (Japan)

    2013-12-15

    Highlights: •LiH can dramatically improve the hydrogen desorption properties of LiNHNH{sub 2}. •KH doping had positive effect in promoting the hydrogen desorption properties of LiNHNH{sub 2}–LiH mixture. •The reaction mechanism between LiNHNH{sub 2} and LiH was studied and discussed. -- Abstract: Lithium hydrazide (LiNHNH{sub 2}), which is a white solid with 8.0 mass% of theoretical hydrogen content, was synthesized from a reaction between anhydrous hydrazine and n-butyllithium in diethyl ether. The thermodynamic properties of this compound and its detailed decomposition pathways had been investigated in our previous work. However, a number of undesired gaseous products such as hydrazine (N{sub 2}H{sub 4}) and ammonia (NH{sub 3}) were generated during the thermal decomposition of LiNHNH{sub 2}. In this work, alkali metal hydride was used to suppress the impurities in the desorbed hydrogen and improved the hydrogen desorption properties. The reaction mechanism between LiNHNH{sub 2} and LiH was also studied and discussed in this paper.

  16. Electrochemistry of ytterbium (III) in molten alkali metal chlorides

    Energy Technology Data Exchange (ETDEWEB)

    Smolenski, V.; Novoselova, A. [Institute of High-Temperature Electrochemistry, Ural Division, Russian Academy of Science, Ekaterinburg, 620219 (Russian Federation); Osipenko, A. [Research Institute of Atomic Reactors, Dimitrovgrad-10, Ulyanovsk Region, 433010 (Russian Federation); Caravaca, C. [High Level Waste Unit, Nuclear Fission Division, CIEMAT, Madrid, 28040 (Spain); Cordoba, G. de [High Level Waste Unit, Nuclear Fission Division, CIEMAT, Madrid, 28040 (Spain)], E-mail: g.cordoba@ciemat.es

    2008-12-30

    This work presents the electrochemical study of Yb(III) ions in molten alkali metal chlorides in the temperature range 723-1073 K. Transient electrochemical techniques such as linear sweep, cyclic and square wave voltammetry, and potentiometry at zero current have been used to investigate the reduction mechanism, transport parameters and thermodynamic properties of the reaction YbCl{sub 2} + 1/2Cl{sub 2} = YbCl{sub 3} The results obtained show that the reduction reaction Yb(III) + e{sup -} {r_reversible} Yb(II) is reversible being controlled by the rate of the mass transfer. The diffusion coefficient of [YbCl{sub 6}]{sup 3-} complex ions has been determined at different temperatures in the fused eutectic LiCl-KCl, the equimolar NaCl-KCl and the CsCl media. The apparent standard potential of the soluble-soluble redox system Yb(III)/Yb(II) has been obtained by cyclic voltammetry. The influence of the nature of the solvent on the electrochemical and thermodynamic properties of ytterbium compounds is discussed.

  17. On the origin of alkali metals in Europa exosphere

    Science.gov (United States)

    Ozgurel, Ozge; Pauzat, Françoise; Ellinger, Yves; Markovits, Alexis; Mousis, Olivier; LCT, LAM

    2016-10-01

    At a time when Europa is considered as a plausible habitat for the development of an early form of life, of particular concern is the origin of neutral sodium and potassium atoms already detected in its exosphere (together with magnesium though in smaller abundance), since these atoms are known to be crucial for building the necessary bricks of prebiotic species. However their origin and history are still poorly understood. The most likely sources could be exogenous and result from the contamination produced by Io's intense volcanism and/or by meteoritic bombardment. These sources could also be endogenous if these volatile elements originate directly from Europa's icy mantle. Here we explore the possibility that neutral sodium and potassium atoms were delivered to the satellite's surface via the upwelling of ices formed in contact with the hidden ocean. These metallic elements would have been transferred as ions to the ocean at early epochs after Europa's formation, by direct contact of water with the rocky core. During Europa's subsequent cooling, the icy layers formed at the top of the ocean would have kept trapped the sodium and potassium, allowing their future progression to the surface and final identification in the exosphere of the satellite. To support this scenario, we have used chemistry numerical models based on first principle periodic density functional theory (DFT). These models are shown to be well adapted to the description of compact ice and are capable to describe the trapping and neutralization of the initial ions in the ice matrix. The process is found relevant for all the elements considered, alkali metals like Na and K, as well as for Mg and probably for Ca, their respective abundances depending essentially of their solubility and chemical capabilities to blend with water ices.

  18. Effects of Heavy Metals and Saline-alkali on Growth, Physiology and Biochemistry of Orychophragmus violaceus

    Institute of Scientific and Technical Information of China (English)

    Xiaoai ZHANG; Zhihui WANG; Xinquan ZHANG; Mingyang Ll; Jing ZUO

    2012-01-01

    Abstract [Oh.jective] The aim was to study on effects of heavy metals and saline-al- kali on growth, physiology and biochemistry of Orychophragmus violaceus. [Method] Taken Orychophragmus violaceus as materials, growth, physiology and biochemistry were explored under stress of saline-alkali and heavy metals (light, moderate and se- vere saline-alkali, Pb, Pb + Cd, light saline-alkali + Pb, moderate saline-alkali + Pb, severe saline-alkali + Pb, light saline-alkali + Pb + Cd, moderate saline-alkali + Pb + Cd and severe saline-alkali + Pb + Cd) with control group set. [Result] Light stress of saline-alkali had little effect on membrane permeability, as follows: MDA contents in leaves and root systems declined by 25.6% and 9.0% compared with control group; Pb (500 mg/L) stress promoted synthetization of photosynthetic pigments, as follows: chlorophyll a and b and carotenoid increased by 0.86%, 0.69% and 6.25% than those of control group; combined stresses of Pb and Cd destroyed synthetization of photosynthetic pigments, among which carotenoid was more sensitive; under com- bined stresses of saline-alkali, Pb and Cd, POD and SOD activities, soluble saccha- rides and Pro content all increased and activities of POD and SOD in root system were both higher than those in leaves. [Conclusion] Orychophragmus violaceus is with resistance against light combined stresses of saline-alkali and Pb (500 mg/L).

  19. Pi resonance of chemisorbed alkali atoms on noble metals.

    Science.gov (United States)

    Borisov, A G; Sametoglu, V; Winkelmann, A; Kubo, A; Pontius, N; Zhao, J; Silkin, V M; Gauyacq, J P; Chulkov, E V; Echenique, P M; Petek, H

    2008-12-31

    We have performed a joint experimental and theoretical study of the unoccupied electronic structure of alkali adsorbates on the (111) surfaces of Cu and Ag. Combining angle- and time-resolved two-photon photoemission spectroscopy with wave packet propagation calculations we show that, along with the well known sigma resonance oriented along the surface normal, there exist long-lived alkali-localized resonances oriented parallel to the surface (pi symmetry). These new resonances are stabilized by the projected band gap of the substrate and emerge primarily from the mixing of the p and d Rydberg orbitals of the free alkali atom modified by the interaction with the surface.

  20. Hydrogen Adsorption by Alkali Metal Graphite Intercalation Compounds

    Science.gov (United States)

    Purewal, Justin

    Adsorption occurs whenever a solid surface is exposed to a gas or liquid, and is characterized by an increase in fluid density near the interface. Adsorbents have drawn attention in the current effort to engineer materials that store hydrogen at high densities within moderate temperature and pressure regimes. Carbon adsorbents are a logical choice as a storage material due to their low costs and large surface areas. Unfortunately, carbon adsorbents suffer from a low binding enthalpy for H2 (about 5 kJ mol-1), well below the 15 to 18 kJ mol-1) that is considered optimal for hydrogen storage systems. Binding interactions can be increased by the following methods: (1) adjusting the graphite interplanar separation with a pillared structure, and (2) introducing dopant species that interact with H2 molecules by strong electrostatic forces. Graphite intercalation compounds are a class of materials that contain both pillared structures and chemical dopants, making them an excellent model system for studying the fundamentals of hydrogen adsorption in nanostructured carbons. Pressure-composition-temperature diagrams of the MC24(H 2)x graphite intercalation compounds were measured for M = (K, Rb, Cs). Adsorption enthalpies were measured as a function of H2 concentration. Notably, CsC24 had an average adsorption enthalpy of 14.9 kJ mol-1), nearly three times larger than that of pristine graphite. The adsorption enthalpies were found to be positively correlated with the alkali metal size. Adsorption capacities were negatively correlated with the size of the alkali metal. The rate of adsorption is reduced at large H2 compositions, due to the effects of site-blocking and correlation on the H2 diffusion. The strong binding interaction and pronounced molecular-sieving behavior of KC24 is likely to obstruct the translational diffusion of adsorbed H2 molecules. In this work, the diffusion of H2 adsorbed in KC24 was studied by quasielastic neutron scattering measurements and molecular

  1. Behavior of Alkali Metals and Ash in a Low-Temperature Circulating Fluidized Bed (LTCFB) Gasifier

    DEFF Research Database (Denmark)

    Narayan, Vikas; Jensen, Peter Arendt; Henriksen, Ulrik Birk

    2016-01-01

    A low-temperature circulating fluidized bed system (LTCFB) gasifier allows for pyrolysis and gasification to occurat low temperatures, thereby improving the retention of alkali and other inorganic elements within the system and minimizingthe amount of ash species in the product gas. In addition......, the low reactor temperature ensures that high-alkali biomass fuels canbe used without risk of bed defluidization. This paper presents the first investigation of the fate of alkali metals and ash in lowtemperaturegasifiers. Measurements on bed material and product gas dust samples were made on a 100 k...

  2. Multi-photon processes in alkali metal vapors

    Science.gov (United States)

    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.

  3. Influence of alkali metal doping on surface properties and catalytic activity/selectivity of CaO catalysts in oxidative coupling of methane

    Institute of Scientific and Technical Information of China (English)

    V.H.Rane; S.T.Chaudhari; V.R.Choudhary

    2008-01-01

    Surface properties (viz. surface area, basicity/base strength distribution, and crystal phases) of alkali metal doped CaO (alkali metal/Ca = 0.1 and 0.4) catalysts and their catalytic activity/selectivity in oxidative coupling of methane (OCM) to higher hydrocarbons at different reaction conditions (viz. temperature, 700 and 750 ℃; CH4/O2 ratio, 4.0 and 8.0 and space velocity, 5140-20550 cm3·g-1·h-1) have been investigated. The influence of catalyst calcination temperature on the activity/selectivity has also been investigated. The surface properties (viz. surface area, basicity/base strength distribution) and catalytic activity/selectivity of the alkali metal doped CaO catalysts are strongly influenced by the alkali metal promoter and its concentration in the alkali metal doped CaO catalysts. An addition of alkali metal promoter to CaO results in a large decrease in the surface area but a large increase in the surface basicity (strong basic sites) and the C2+ selectivity and yield of the catalysts in the OCM process. The activity and selectivity are strongly influenced by the catalyst calcination temperature. No direct relationship between surface basicity and catalytic activity/selectivity has been observed. Among the alkali metal doped CaO catalysts, Na-CaO (Na/Ca = 0.1, before calcination) catalyst (calcined at 750 ℃), showed best performance (C2+selectivity of 68.8% with 24.7% methane conversion), whereas the poorest performance was shown by the Rb-CaO catalyst in the OCM process.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  6. Properties of alkali metal atoms deposited on a MgO surface: a systematic experimental and theoretical study.

    Science.gov (United States)

    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.

  7. Hyperfine-frequency shifts of alkali-metal atoms during long-range collisions

    CERN Document Server

    McGuyer, B H

    2013-01-01

    Collisions with chemically inert atoms or molecules change the hyperfine coupling of an alkali-metal atom through the hyperfine-shift interaction. This interaction is responsible for the pressure shifts of the microwave resonances of alkali-metal atoms in buffer gases, is an important spin interaction in alkali-metal--noble-gas van der Waals molecules, and is anticipated to enable the magnetoassociation of ultracold molecules such as RbSr. An improved estimate is presented for the long-range asymptote of this interaction for Na, K, Rb, and Cs. To test the results, the change in hyperfine coupling due to a static electric field is estimated and reasonable agreement is found.

  8. Ionic conductivity of polymer gels deriving from alkali metal ionic liquids and negatively charged polyelectrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Ogihara, Wataru; Yoshizawa, Masahiro; Ohno Hiroyuki [Tokyo University of Agriculture and Technology (Japan). Dept. of Biotechnology; Sun, Jiazeng; Forsyth, M. [Monash University, Clayton (Australia). School of Materials Engineering; MacFarlane, D.R. [Monash University, Clayton (Australia). School of Chemistry

    2004-04-30

    We have prepared polymer gel electrolytes with alkali metal ionic liquids (AMILs) that inherently contain alkali metal ions. The AMIL consisted of sulfate anion, imidazolium cation, and alkali metal cation. AMILs were mixed directly with poly(3-sulfopropyl acrylate) lithium salt or poly(2-acrylamido-2-methylpropanesulfonic acid) lithium salt to form polymer gels. The ionic conductivity of these gels decreased with increasing polymer fraction, as in general ionic liquid/polymer mixed systems. At low polymer concentrations, these gels displayed excellent ionic conductivity of 10{sup -4} to 10{sup -3} S cm{sup -1} at room temperature. Gelation was found to cause little change in the {sup 7}Li diffusion coefficient of the ionic liquid, as measured by pulse-field-gradient NMR. These data strongly suggest that the lithium cation migrates in successive pathways provided by the ionic liquids. (author)

  9. A hetero-alkali-metal version of the utility amide LDA: lithium-potassium diisopropylamide.

    Science.gov (United States)

    Armstrong, David R; Kennedy, Alan R; Mulvey, Robert E; Robertson, Stuart D

    2013-03-14

    Designed to extend the synthetically important alkali-metal diisopropylamide [N(i)Pr(2); DA] class of compounds, the first example of a hetero-alkali-metallic complex of DA has been prepared as a partial TMEDA solvate. Revealed by an X-ray crystallographic study, its structure exists as a discrete lithium-rich trinuclear Li(2)KN(3) heterocycle, with TMEDA only solvating the largest of the alkali-metals, with the two-coordinate lithium atoms being close to linearity [161.9(2)°]. A variety of NMR spectroscopic studies, including variable temperature and DOSY NMR experiments, suggests that this new form of LDA maintains its integrity in non-polar hydrocarbon solution. This complex thus represents a rare example of a KDA molecule which is soluble in non-polar medium without the need for excessive amounts of solubilizing Lewis donor being added.

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

    Science.gov (United States)

    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.

  11. In Situ Measurement of Alkali Metals in an MSW Incinerator Using a Spontaneous Emission Spectrum

    Directory of Open Access Journals (Sweden)

    Weijie Yan

    2017-03-01

    Full Text Available This paper presents experimental investigations of the in situ diagnosis of the alkali metals in the municipal solid waste (MSW flame of an industrial grade incinerator using flame emission spectroscopy. The spectral radiation intensities of the MSW flame were obtained using a spectrometer. A linear polynomial fitting method is proposed to uncouple the continuous spectrum and the characteristic line. Based on spectra processing and a non-gray emissivity model, the flame temperature, emissivity, and intensities of the emission of alkali metals were calculated by means of measuring the spectral radiation intensities of the MSW flame. Experimental results indicate that the MSW flame contains alkali metals, including Na, K, and even Rb, and it demonstrates non-gray characteristics in a wavelength range from 500 nm to 900 nm. Peak intensities of the emission of the alkali metals were found to increase when the primary air was high, and the measured temperature varied in the same way as the primary air. The temperature and peak intensities of the lines of emission of the alkali metals may be used to adjust the primary airflow and to manage the feeding of the MSW to control the alkali metals in the MSW flame. It was found that the peak intensity of the K emission line had a linear relationship with the peak intensity of the Na emission line; this correlation may be attributed to their similar physicochemical characteristics in the MSW. The variation trend of the emissivity of the MSW flame and the oxygen content in the flue gas were almost opposite because the increased oxygen content suppressed soot formation and decreased soot emissivity. These results prove that the flame emission spectroscopy technique is feasible for monitoring combustion in the MSW incinerator in situ.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  14. Density functional theory based screening of ternary alkali-transition metal borohydrides: A computational material design project

    DEFF Research Database (Denmark)

    Hummelshøj, Jens Strabo; Landis, David; Voss, Johannes

    2009-01-01

    We present a computational screening study of ternary metal borohydrides for reversible hydrogen storage based on density functional theory. We investigate the stability and decomposition of alloys containing 1 alkali metal atom, Li, Na, or K (M1); and 1 alkali, alkaline earth or 3d/4d transition...

  15. Surface phonons on Al(111) surface covered by alkali metals

    Science.gov (United States)

    Rusina, G. G.; Eremeev, S. V.; Borisova, S. D.; Sklyadneva, I. Yu.; Chulkov, E. V.

    2005-06-01

    We investigated the vibrational and structural properties of the Al(111)-(3×3)R30°-AM (AM=Na,K,Li) adsorbed systems using interaction potentials from the embedded-atom method. The surface relaxation, surface phonon dispersion, and polarization of vibrational modes for the alkali adatoms and the substrate atoms as well as the local density of states are discussed. Our calculated structural parameters are in close agreement with experimental and ab initio results. The obtained vibrational frequencies compare fairly well with the available experimental data.

  16. Synthetic, structural, and theoretical investigations of alkali metal germanium hydrides--contact molecules and separated ions.

    Science.gov (United States)

    Teng, Weijie; Allis, Damian G; Ruhlandt-Senge, Karin

    2007-01-01

    The preparation of a series of crown ether ligated alkali metal (M=K, Rb, Cs) germyl derivatives M(crown ether)nGeH3 through the hydrolysis of the respective tris(trimethylsilyl)germanides is reported. Depending on the alkali metal and the crown ether diameter, the hydrides display either contact molecules or separated ions in the solid state, providing a unique structural insight into the geometry of the obscure GeH3- ion. Germyl derivatives displaying M--Ge bonds in the solid state are of the general formula [M([18]crown-6)(thf)GeH3] with M=K (1) and M=Rb (4). The compounds display an unexpected geometry with two of the GeH3 hydrogen atoms closely approaching the metal center, resulting in a partially inverted structure. Interestingly, the lone pair at germanium is not pointed towards the alkali metal, rather two of the three hydrides are approaching the alkali metal center to display M--H interactions. Separated ions display alkali metal cations bound to two crown ethers in a sandwich-type arrangement and non-coordinated GeH3- ions to afford complexes of the type [M(crown ether)2][GeH3] with M=K, crown ether=[15]crown-5 (2); M=K, crown ether=[12]crown-4 (3); and M=Cs, crown ether=[18]crown-6 (5). The highly reactive germyl derivatives were characterized by using X-ray crystallography, 1H and 13C NMR, and IR spectroscopy. Density functional theory (DFT) and second-order Møller-Plesset perturbation theory (MP2) calculations were performed to analyze the geometry of the GeH3- ion in the contact molecules 1 and 4.

  17. Phonon dispersion in alkali metals and their equiatomic sodium-based binary alloys

    Institute of Scientific and Technical Information of China (English)

    Aditya M. VORA

    2008-01-01

    In the present article, the theoretical calcula-tions of the phonon dispersion curves (PDCs) of five alkali metals viz. Li, Na, K, Rb, Cs and their four equia-tomic sodium-based binary alloys viz. Na0.5Li0.5,Na0.5K0.5, Na0.5Rb0.5 and Na0.5Cs0.5 to second order in a local model potential is discussed in terms of the real-space sum of the Born yon Karman central force con-stants. Instead of the concentration average of the force constants of pure alkali metals, the pseudo-alloy-atom (PAA) is adopted to directly compute the force constants of the four equiatomic sodium based binary alloys and was successfully applied. The exchange and correlation functions due to the Hartree (H) and Ichimaru-Utsumi (IU) are used to investigate the influence of the screening effects. The phonon frequencies of alkali metals and their four equiatomic sodium-based binary alloys in the longit-udinal branch are more sensitive to the exchange and cor-relation effects in comparison with the transverse branches. The PDCs of pure alkali metals are found in qualitative agreement with the available experimental data. The frequencies in the longitudinal branch are sup-pressed rather due to IU-screening function than those due to static H-screening function.

  18. Absorption Spectroscopy of Rubidium in an Alkali Metal Dispenser Cell and Bleached Wave Analysis

    Science.gov (United States)

    2015-03-26

    resulted in a transmission too low below the detection limit of the photodiodes. When the current ceased, the spectrum almost immediately returned to a...absorption spectrum of a rubidium alkali metal dispenser (AMD) cell was obtained in order to determine the system’s suitability for use in a diode ...18 8. Cell Pressure vs. Required Current .............................................................................. 20 9. Time vs. Rubidium

  19. Long-range interactions between excited helium and alkali-metal atoms

    KAUST Repository

    Zhang, J.-Y.

    2012-12-03

    The dispersion coefficients for the long-range interaction of the first four excited states of He, i.e., He(2 1,3S) and He(2 1,3P), with the low-lying states of the alkali-metal atoms Li, Na, K, and Rb are calculated by summing over the reduced matrix elements of the multipole transition operators. For the interaction between He and Li the uncertainty of the calculations is 0.1–0.5%. For interactions with other alkali-metal atoms the uncertainty is 1–3% in the coefficient C5, 1–5% in the coefficient C6, and 1–10% in the coefficients C8 and C10. The dispersion coefficients Cn for the interaction of He(2 1,3S) and He(2 1,3P) with the ground-state alkali-metal atoms and for the interaction of He(2 1,3S) with the alkali-metal atoms in their first 2P states are presented in this Brief Report. The coefficients for other pairs of atomic states are listed in the Supplemental Material.

  20. Lanthanide Single-Molecule Magnets Framed by Alkali Metals & Magnetic and Spectroscopic Studies of 3d Transition Metal Complexes

    DEFF Research Database (Denmark)

    Konstantatos, Andreas

    )imino)- methyl)benzene-1,2-diol]. Using this ligand, we were able to synthesize four different families of lanthanide complexes framed by alkali metals. Throughout the chapter we demonstrate how we can exploit the presence of the coordinated alkali metal ions in order to induce changes to the structure....... In Chapter 3 we present the results of our work with third row (3d) transition metal ions and their complexes. Specifically, in section 2.1 we report a series of complexes synthesized using a tripodal hexadentate Schiff-base ligand. The ligand demonstrates the ability to form mononuclear or trinuclear...... complexes of M3+ or M2+ metal ions (M: 3d transition metal) with the preference to either approximate octahedral or trigonal prismatic coordination geometry. A detailed magnetic characterization for most of the complexes is presented where a trinuclear Co2+ cluster stands out for its pronounced SMM...

  1. Alkali metal cation doping of metal-organic framework for enhancing carbon dioxide adsorption capacity

    Institute of Scientific and Technical Information of China (English)

    Yan Cao; Yunxia Zhao; Fujiao Song; Qin Zhong

    2014-01-01

    Metal-organic frameworks (MOFs) have attracted much attention as adsorbents for the separation of CO2 from flue gas or natural gas. Here, a typical metal-organic framework HKUST-1(also named Cu-BTC or MOF-199) was chemically reduced by doping it with alkali metals (Li, Na and K) and they were further used to investigate their CO2 adsorption capacities. The structural information, surface chemistry and thermal behavior of the prepared adsorbent samples were characterized by X-ray powder diffraction (XRD), thermo-gravimetric analysis (TGA) and nitrogen adsorption-desorption isotherm analysis. The results showed that the CO2 storage capacity of HKUST-1 doped with moderate quantities of Li+, Na+ and K+, individually, was greater than that of unmodified HKUST-1. The highest CO2 adsorption uptake of 8.64 mmol/g was obtained with 1K-HKUST-1, and it was ca. 11%increase in adsorption capacity at 298 K and 18 bar as compared with HKUST-1. Moreover, adsorption tests showed that HKUST-1 and 1K-HKUST-1 displayed much higher adsorption capacities of CO2 than those of N2. Finally, the adsorption/desorption cycle experiment revealed that the adsorption performance of 1K-HKUST-1 was fairly stable, without obvious deterioration in the adsorption capacity of CO2 after 10 cycles.

  2. Device and method for upgrading petroleum feedstocks and petroleum refinery streams using an alkali metal conductive membrane

    Energy Technology Data Exchange (ETDEWEB)

    Gordon, John Howard; Alvare, Javier

    2016-09-13

    A reactor has two chambers, namely an oil feedstock chamber and a source chamber. An ion separator separates the oil feedstock chamber from the source chamber, wherein the ion separator allows alkali metal ions to pass from the source chamber, through the ion separator, and into the oil feedstock chamber. A cathode is at least partially housed within the oil feedstock chamber and an anode is at least partially housed within the source chamber. A quantity of an oil feedstock is within the oil feedstock chamber, the oil feedstock comprising at least one carbon atom and a heteroatom and/or one or more heavy metals, the oil feedstock further comprising naphthenic acid. When the alkali metal ion enters the oil feedstock chamber, the alkali metal reacts with the heteroatom, the heavy metals and/or the naphthenic acid, wherein the reaction with the alkali metal forms inorganic products.

  3. The different poisoning behaviors of various alkali metal containing compounds on SCR catalyst

    Science.gov (United States)

    Du, Xuesen; Yang, Guangpeng; Chen, Yanrong; Ran, Jingyu; Zhang, Li

    2017-01-01

    Alkali metals are poisonous to the metal oxide catalyst for NO removal. The chemical configuration of alkali containing substance and interacting temperature can affect the poisoning profile. A computational method based on Frontier Molecular Orbital analysis was proposed to determine the reacting behavior of various alkali-containing substances with SCR catalyst. The results reveal that the poisoning reactivities of various substances can be ranked as: E (MOH) > E (M2SO4) > E(MCl) > E(MNO3) > E(MHSO4). The experimental activity tests of the catalysts calcined at stepped temperatures show that NaOH can react with the catalyst below 200 °C. NaCl and NaNO3 start to react with the catalyst at a temperature between 300 and 400 °C. Unlike MOH, MCl and MNO3, which can produce volatile or decomposable species for the anions after reacting with the catalyst, M2SO4 and MHSO4 will leave both cations and anions on the catalyst surface. The sulfate ions left on the catalyst can generate active acid sites for NH3 adsorption. The experimental results also show that Na2SO4 and NaHSO4 will not lower the NO conversion. The after-reaction influences of various alkali metals were studied using theoretical and experimental methods. The theoretical results show that the acidity decreases with doping of alkali metal. Experiments show a consistent result that the NO conversion decreases as undoped >LiCl > NaCl > KCl.

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

    Science.gov (United States)

    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.

  5. Speciation of phytate ion in aqueous solution. Alkali metal complex formation in different ionic media.

    Science.gov (United States)

    De Stefano, Concetta; Milea, Demetrio; Pettignano, Alberto; Sammartano, Silvio

    2003-08-01

    The acid-base properties of phytic acid [ myo-inositol 1,2,3,4,5,6-hexakis(dihydrogen phosphate)] (H(12)Phy; Phy(12-)=phytate anion) were studied in aqueous solution by potentiometric measurements ([H+]-glass electrode) in lithium and potassium chloride aqueous media at different ionic strengths (0iodide (Et(4)NI; e.g., at I=0.5 mol L(-1), log K(3)(H)=11.7, 8.0, 9.1, and 9.1 in Et(4)NI, LiCl, NaCl and KCl, respectively; the protonation constants in Et(4)NI and NaCl were already reported), owing to the strong interactions occurring between the phytate and alkaline cations present in the background salt. We explained this in terms of complex formation between phytate and alkali metal ions. Experimental evidence allows us to consider the formation of 13 mixed proton-metal-ligand complexes, M(j)H(i)Phy((12-i-j)-), (M+ =Li+, Na+, K+), with jstability of alkali metal complexes follows the trend Li+ > or =Na+K+. Some measurements were also performed at constant ionic strength (I=0.5 mol L(-1)), using different mixtures of Et(4)NI and alkali metal chlorides, in order to confirm the formation of hypothesized and calculated metal-proton-ligand complex species and to obtain conditional protonation constants in these multi-component ionic media.

  6. Electrodeposition of alkali and alkali-earth metals on liquid lead cathodes in molten salts

    Energy Technology Data Exchange (ETDEWEB)

    Caravaca, C.; De Cordoba, G. [CIEMAT/DE/DFN/URAA. Avda. Complutense, 22. 28040 Madrid (Spain)

    2008-07-01

    Pyrochemical processing of spent nuclear fuel leads to the dissolution as chlorides of fission products (FPs) that have to be removed in order to recycle the salt. Precipitation technique have been tested for the removal of these FPs in the LiCl-KCl, salt selected as reference, with different results. Salt decontamination from lanthanides can be easily achieved as solid precipitates of oxychlorides or single phosphates; however, for the alkaline and alkaline-earth metals this technique is not suitable. Within the EUROPART project (VI FP of the EC), a new route that consist of the electrodeposition of these FP on a liquid lead cathode (LLC) has been considered, including the Li and K constituting the electrolyte. First results obtained with Sr and Cs are presented herein. Although according to the thermodynamic potential values, the electrodeposition order on LLC is Ba, Sr, Li, K and Cs, during our experiments it was not possible to distinguish the electrochemical signals corresponding to the individual elements. (authors)

  7. Alkali-crown ether complexes at metal surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Thontasen, Nicha; Deng, Zhitao; Rauschenbach, Stephan [Max Planck Institute for Solid State Research, Stuttgart (Germany); Levita, Giacomo [University of Trieste, Trieste (Italy); Malinowski, Nikola [Max Planck Institute for Solid State Research, Stuttgart (Germany); Bulgarian Academy of Sciences, Sofia (Bulgaria); Kern, Klaus [Max Planck Institute for Solid State Research, Stuttgart (Germany); EPFL, Lausanne (Switzerland)

    2010-07-01

    Crown ethers are polycyclic ethers which, in solution, selectively bind cations depending on the size of the ring cavity. The study of a single host-guest complex is highly desirable in order to reveal the characteristics of these specific interactions at the atomic scale. Such detailed investigation is possible at the surface where high resolution imaging tools like scanning tunneling microscopy (STM) can be applied. Here, electrospray ion beam deposition (ES-IBD) is employed for the deposition of Dibenzo-24-crown-8 (DB24C8)-H{sup +}, -Na{sup +} and -Cs{sup +} complexes on a solid surface in ultrahigh vacuum (UHV). Where other deposition techniques have not been successful, this deposition technique combines the advantages of solution based preparation of the complex ions with a highly clean and controlled deposition in UHV. Single molecular structures and the cation-binding of DB24C8 at the surface are studied in situ by STM and MALDI-MS (matrix assisted laser desorption ionization mass spectrometry). The internal structure of the complex, i.e. ring and cavity, is observable only when alkali cations are incorporated. The BD24C8-H{sup +} complex in contrast appears as a compact feature. This result is in good agreement with theoretical models based on density functional theory calculations.

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

    Science.gov (United States)

    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.

  9. Tuning the work function of ultrathin oxide films on metals by adsorption of alkali atoms.

    Science.gov (United States)

    Martinez, Umberto; Giordano, Livia; Pacchioni, Gianfranco

    2008-04-28

    We report a theoretical investigation of the adsorption of alkali metal atoms deposited on ultrathin oxide films. The properties of Li, Na, and K atoms adsorbed on SiO(2)/Mo(112) and of K on MgO / Ag(100) and TiO(2)/Pt(111) have been analyzed with particular attention to the induced changes in the work function of the system, Phi. On the nonreducible SiO(2) and MgO oxide films there is a net transfer of the outer ns electron of the alkali atom to the metal substrate conduction band; the resulting surface dipole substantially lowers Phi. The change in Phi depends (a) on the adsorption site (above the oxide film or at the interface) and (b) on the alkali metal coverage. Deposition of K on reducible TiO(2) oxide films results in adsorbed K(+) ions and in the formation of Ti(3+) ions. No charge transfer to the metal substrate is observed but also in this case the surface dipole resulting from the K-TiO(2) charge transfer has the effect to considerably reduce the work function of the system.

  10. Development and testing of on-line analytical instrumentation for alkali and heavy metal release in pressurised conversion processes

    Energy Technology Data Exchange (ETDEWEB)

    Hernberg, R.; Haeyrinen, V.; Oikari, R. [Tampere Univ. of Technology (Finland)

    1997-10-01

    The purpose of the project is to demonstrate in industrial conditions and further develop the continuous alkali measurement method plasma excited alkali resonance line spectroscopy (PEARLS) developed at Tampere University of Technology (TUT). The demonstration takes place in joint measuring campaigns, where two other continuous alkali measurement methods, ELIF and surface ionisation, are being simultaneously demonstrated. A modification of PEARLS will also be developed for the continuous measurement of heavy metal concentrations. A market study of continuous measuring techniques for alkali and heavy metals is further part of the project. The method will be demonstrated in two pressurised fluidised bed combustion facilities. One of these is the 10 MW PCFB of Foster Wheeler Energia Oy in Karhula. The second one is yet to be decided. The first measuring campaign is scheduled for the spring of 1997 in Karhula. In 1996 the group at TUT participated in the performance of a market study regarding continuous measuring techniques for alkali and heavy metal concentrations. A draft report was submitted to and approved by the EC. Development work on PEARLS in 1996 has centered around the construction of a calibration device for alkali measurements. The device can be used by all three measuring techniques in the project to check readings against a known alkali concentration at controlled and known conditions. In 1996 PEARLS was applied for alkali measurement at several pressurised combustion installations of laboratory and industrial pilot scale

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

    Science.gov (United States)

    Lutz, Jesse J; Hutson, Jeremy M

    2014-01-07

    We investigate the potential energy surfaces and activation energies for reactions between methyl halide molecules CH3X (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, CH3X + A → CH3 + 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.

  12. "Doubly magic" conditions in magic-wavelength trapping of ultracold alkali-metal atoms.

    Science.gov (United States)

    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.

  13. Emission Channeling Studies of the Lattice Site of Oversized Alkali Atoms Implanted in Metals

    CERN Multimedia

    2002-01-01

    % IS340 \\\\ \\\\ As alkali atoms have the largest atomic radius of all elements, the determination of their lattice configuration following implantation into metals forms a critical test for the various models predicting the lattice site of implanted impurity atoms. The site determination of these large atoms will especially be a crucial check for the most recent model that relates the substitutional fraction of oversized elements to their solution enthalpy. Recent exploratory $^{213}$Fr and $^{221}$Fr $\\alpha$-emission channeling experiments at ISOLDE-CERN and hyperfine interaction measurements on Fr implanted in Fe gave an indication for anomalously large substitutional fractions. To investigate further the behaviour of Fr and other alkali atoms like Cs and Rb thoroughly, more on-line emission channeling experiments are needed. We propose a number of shifts for each element, where the temperature of the implanted metals will be varied between 50$^\\circ$ and 700$^\\circ$~K. Temperature dependent measurements wi...

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

    Energy Technology Data Exchange (ETDEWEB)

    Matsuda, K., E-mail: kazuhiro-matsuda@scphys.kyoto-u.ac.jp; Fukumaru, T.; Kimura, K.; Yao, M. [Graduate School of Science, Kyoto University, Kyoto 606-8502 (Japan); Tamura, K. [Graduate School of Engineering, Kyoto University, Kyoto 606-8502 (Japan); Katoh, M. [A.L.M.T. Corp., Iwasekoshi-Machi 2, Toyama 931-8543 (Japan); Kajihara, Y.; Inui, M. [Graduate School of Integrated Arts and Sciences, Hiroshima University, Higashi-Hiroshima 739-8521 (Japan); Itou, M.; Sakurai, Y. [Japan Synchrotron Radiation Research Institute, SPring-8, 1-1-1 Kouto, Sayo, Hyogo 679-5198 (Japan)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  16. The 3-Dimensional q-Deformed Harmonic Oscillator and Magic Numbers of Alkali Metal Clusters

    CERN Document Server

    Bonatsos, Dennis; Raychev, P P; Roussev, R P; Terziev, P A; Bonatsos, Dennis

    1999-01-01

    Magic numbers predicted by a 3-dimensional q-deformed harmonic oscillator with Uq(3) > SOq(3) symmetry are compared to experimental data for alkali metal clusters, as well as to theoretical predictions of jellium models, Woods--Saxon and wine bottle potentials, and to the classification scheme using the 3n+l pseudo quantum number. The 3-dimensional q-deformed harmonic oscillator correctly predicts all experimentally observed magic numbers up to 1500 (which is the expected limit of validity for theories based on the filling of electronic shells), thus indicating that Uq(3), which is a nonlinear extension of the U(3) symmetry of the spherical (3-dimensional isotropic) harmonic oscillator, is a good candidate for being the symmetry of systems of alkali metal clusters.

  17. Investigation of Anti-Relaxation Coatings for Alkali-Metal Vapor Cells Using Surface Science Techniques

    OpenAIRE

    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.; Kimball, D. F. Jackson; C. Jaye; Karaulanov, T.; Narducci, F. A.; Rangwala, S. A.; Robinson, H. G.

    2010-01-01

    Many technologies based on cells containing alkali-metal atomic vapor benefit from the use of anti-relaxation 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 stu...

  18. Investigation of anti-Relaxation coatings for alkali-metal vapor cells using surface science techniques

    OpenAIRE

    Seltzer, S. J.

    2011-01-01

    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 stud...

  19. Orbital Magnetism and Dynamics in Alkali Metal Clusters

    CERN Document Server

    Nesterenko, V O; De Souza-Cruz, F F; Marinelli, J R

    2000-01-01

    Two remarkable orbital magnetic resonances, M1 scissor mode and M2 twist mode, are predicted in deformed and spherical metal clusters, respectively. We show that these resonances provide a valuable information about many cluster properties (quadrupole deformation, magnetic susceptibility, single-particle spectrum, etc.)

  20. Alkali metal and simple gas atom adsorption and coadsorption on transition metal surfaces

    CERN Document Server

    Norris, A G

    2000-01-01

    system is formed by adsorption of potassium or cesium on the Ni(100)c(2x2)-O overlayer. The difficulty of the structural fit is compounded' by the size of the unit cell. In this study, Anomalous Scattering was used to investigate whether there is a contribution from the nickel substrate to the reconstruction. Measurements of the fractional order rods at 10 eV and 200 eV below the nickel K edge (8333 eV) showed no discernible differences and involvement of the nickel substrate in the reconstruction can be eliminated. Alkali metal coadsorption systems represent a step along the pathway from simple model adsorbate overlayers to more technologically relevant real systems. Such is their complexity, however, that very few systems have been solved structurally. Presented here are SXRD and STM investigations of two such systems. The first study involves potassium adsorption on the Ni(100)(2x2)p4g-N surface, where a clock reconstruction is present with the nickel substrate atoms rotated in alternate clockwise and anti...

  1. Spinel Metal Oxide-Alkali Carbonate-Based, Low-Temperature Thermochemical Cycles for Water Splitting and CO_2 Reduction

    OpenAIRE

    Xu, Bingjun; Bhawe, Yashodhan; Davis, Mark E.

    2013-01-01

    A manganese oxide-based, thermochemical cycle for water splitting below 1000 °C has recently been reported. The cycle involves the shuttling of Na+ into and out of manganese oxides via the consumption and formation of sodium carbonate, respectively. Here, we explore the combinations of three spinel metal oxides and three alkali carbonates in thermochemical cycles for water splitting and CO_2 reduction. Hydrogen evolution and CO_2 reduction reactions of metal oxides with a given alkali carbona...

  2. Unraveling the absorption spectra of alkali metal atoms attached to helium nanodroplets.

    Science.gov (United States)

    Bünermann, Oliver; Droppelmann, Georg; Hernando, Alberto; Mayol, Ricardo; Stienkemeier, Frank

    2007-12-13

    The absorption spectra of the first electronic exited state of alkali metal atoms on helium nanodroplets formed of both 4He and 3He isotopes were studied experimentally as well as theoretically. In the experimental part new data on the 2palkali metal atoms with helium nanodroplets, a model calculation was performed. New helium density profiles as well as a refined model allowed us to achieve good agreement with the experimental findings. For the first time the red-shifted intensities in the lithium and sodium spectra are explained in terms of enhanced binding configurations in the excited state displaced spatially from the ground state configurations.

  3. Superconductivity and electrical resistivity in alkali metal doped fullerides: Phonon mechanism

    Indian Academy of Sciences (India)

    Dinesh Varshney; A Dube; K K Choudhary; R K Singh

    2005-04-01

    We consider a two-peak model for the phonon density of states to investigate the nature of electron pairing mechanism for superconducting state in fullerides. We first study 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. Electronic parameter as repulsive parameter and the attractive coupling strength are obtained within the random phase approximation. Transition temperature, c, 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 c (≈ 20 K). The superconducting pairing is mainly driven by the high frequency intramolecular phonons and their effects enhance it to 22 K. To illustrate the usefulness of the above approach, the carbon isotope exponent and the pressure effect are also estimated. Temperature dependence of electrical resistivity is then analysed within the same model phonon spectrum. It is inferred from the two-peak model for phonon density of states that high frequency intramolecular phonon modes play a major role in pairing mechanism with possibly some contribution from alkali-C60 phonon to describe most of the superconducting and normal state properties of doped fullerides.

  4. Alkali metal mediated C-C bond coupling reaction.

    Science.gov (United States)

    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)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.

  5. Investigation of Anti-Relaxation Coatings for Alkali-Metal Vapor Cells Using Surface Science Techniques

    CERN Document Server

    Seltzer, S J; Donaldson, M H; Balabas, M V; Barber, S K; Bernasek, S L; Bouchiat, M -A; Hexemer, A; Hibberd, A M; Kimball, D F Jackson; Jaye, C; Karaulanov, T; Narducci, F A; Rangwala, S A; Robinson, H G; Voronov, D L; Yashchuk, V V; Pines, A; Budker, D

    2010-01-01

    Many technologies based on cells containing alkali-metal atomic vapor benefit from the use of anti-relaxation 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 present a survey of modern surface science techniques applied 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. Experimental results include the determination that crystallinity of the coating material is unnecessary, and the detection of C=C double bonds present with...

  6. Impurity detection in alkali-metal vapor cells via nuclear magnetic resonance

    Science.gov (United States)

    Patton, B.; Ishikawa, K.

    2016-11-01

    We use nuclear magnetic resonance spectroscopy of alkali metals sealed in glass vapor cells to perform in situ identification of chemical contaminants. The alkali Knight shift varies with the concentration of the impurity, which in turn varies with temperature as the alloy composition changes along the liquidus curve. Intentional addition of a known impurity validates this approach and reveals that sodium is often an intrinsic contaminant in cells filled with distilled, high-purity rubidium or cesium. Measurements of the Knight shift of the binary Rb-Na alloy confirm prior measurements of the shift's linear dependence on Na concentration, but similar measurements for the Cs-Na system demonstrate an unexpected nonlinear dependence of the Knight shift on the molar ratio. This non-destructive approach allows monitoring and quantification of ongoing chemical processes within the kind of vapor cells which form the basis for precise sensors and atomic frequency standards.

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

    Science.gov (United States)

    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. The vibrational FT-IR (in KBr and ATR techniques) and (1)H and (13)C 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Natesan, K.; Rink, D.L.; Haglund, R.; Clark, R.W. [Argonne National Lab., IL (United States)

    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.

  9. Surface Morphology and Structure of Double-Phase Magnetic Alkali Borosilicate Glasses

    Science.gov (United States)

    Andreeva, N. V.; Naberezhnov, A. A.; Tomkovich, M. V.; Nacke, B.; Kichigin, V.; Rudskoy, A. I.; Filimonov, A. V.

    2016-11-01

    The surface morphology of double-phase magnetic alkali borosilicate glasses of four types obtained by induction melting is studied by the methods of atomic-force and scanning electron microscopy. The distribution of elements over the surface and the elemental composition of the glasses are determined. It is shown that a dendritic system of interrelated channels required for formation of porous matrixes with controlled mean pore diameter may be obtained in these objects depending on the heat treatment mode.

  10. Heavy main-group iodometallates hybridized by alkali metal via 1,10-Phenanthroline-5,6-dione

    Indian Academy of Sciences (India)

    Mengfan Yin; Gengxing Cai; Peng Wang; Xihui Chao; Jibo Liu; Haohong Li; Zhirong Chen

    2015-09-01

    Alkali metals were introduced into heavy main-group iodometallates to get two new IA/IVAheterometallic frameworks [PbI3K(pdon)(H2O)2] (1) and {[Pb3I9K2(pdon)2(H3O)]·H2O} (2) (pdon=1,10-phenanthroline-5,6-dione), which were obtained as single phases by hydrothermal method at different pH values. Compounds 1 and 2 are three-dimensional heterometallic frameworks constructed from the linkage of pdon ligand between iodometallate chains and potassium oxides/iodide clusters. Specially, these two heterometallic frameworks exhibit broadened absorption bands at 700 and 750 nm compared with those of bulk PbI2 and pdon ligand. The band gap of 2 is wider than that of 1, which is due to the absence of · · · interaction in 2. Their thermal stabilities are also discussed.

  11. The influence of chlorine on the fate and activity of alkali metals during the gasification of wood

    Energy Technology Data Exchange (ETDEWEB)

    Struis, R.; Scala, C. von; Schuler, A.; Stucki, S. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1999-08-01

    Chlorine clearly inhibits the CO{sub 2}-gasification reaction of charcoal at 800{sup o}C. From this and other observations the picture emerges that the reduction in the gasification reactivity of the charcoal is intimately related to the deactivation of the catalytically active alkali metals residing in the wood due to the formation of the chloride salt. It is argued that the heavy metal chlorides will likely transfer the chlorine to the indigenous alkali metals during the pyrolysis stage of the wood. The fate of the thus formed alkali metal chlorides can then be either their removal from the sample (evaporation), or, when present at the gasification stage, re-activation (i.e., de-chlorination) under our gasification conditions. (author) 3 figs., 4 refs.

  12. Thermochemical ablation therapy of VX2 tumor using a permeable oil-packed liquid alkali metal.

    Directory of Open Access Journals (Sweden)

    Ziyi Guo

    Full Text Available Alkali metal appears to be a promising tool in thermochemical ablation, but, it requires additional data on safety is required. The objective of this study was to explore the effectiveness of permeable oil-packed liquid alkali metal in the thermochemical ablation of tumors.Permeable oil-packed sodium-potassium (NaK was prepared using ultrasonic mixing of different ratios of metal to oil. The thermal effect of the mixture during ablation of muscle tissue ex vivo was evaluated using the Fluke Ti400 Thermal Imager. The thermochemical effect of the NaK-oil mixture on VX2 tumors was evaluated by performing perfusion CT scans both before and after treatment in 10 VX2 rabbit model tumors. VX2 tumors were harvested from two rabbits immediately after treatment to assess their viability using trypan blue and hematoxylin and eosin (H.E. staining.The injection of the NaK-oil mixture resulted in significantly higher heat in the ablation areas. The permeable oil controlled the rate of heat released during the NaK reaction with water in the living tissue. Perfusion computed tomography and its parameter map confirmed that the NaK-oil mixture had curative effects on VX2 tumors. Both trypan blue and H.E. staining showed partial necrosis of the VX2 tumors.The NaK-oil mixture may be used successfully to ablate tumor tissue in vivo. With reference to the controlled thermal and chemical lethal injury to tumors, using a liquid alkali in ablation is potentially an effective and safe method to treat malignant tumors.

  13. Electric dipole polarizabilities of Rydberg states of alkali-metal atoms

    Science.gov (United States)

    Yerokhin, V. A.; Buhmann, S. Y.; Fritzsche, S.; Surzhykov, A.

    2016-09-01

    Calculations of the static electric-dipole scalar and tensor polarizabilities are presented for two alkali-metal atoms, Rb and Cs, for the n S , n P½,3 /2 , and n D3 /2 ,5 /2 states with large principal quantum numbers up to n =50 . The calculations are performed within an effective one-electron approximation, based on the Dirac-Fock Hamiltonian with a semiempirical core-polarization potential. The obtained results are compared with those from a simpler semiempirical approach and with available experimental data.

  14. Antiproton and proton collisions with the alkali-metal atoms Li, Na, and K

    DEFF Research Database (Denmark)

    Lühr, Armin Christian; Saenz, Alejandro

    2008-01-01

    Single-electron ionization and excitation cross sections as well as cross sections for excitation into the first excited p state of the alkali-metal atoms Li(2s), Na(3s), and K(4s) colliding with antiprotons and protons were calculated using a time-dependent channel-coupling approach....... For antiprotons an impact-energy range from 0.25 to 1000 keV and for protons from 2 to 1000 keV was considered. The target atoms are treated as effective one-electron systems using a model potential. The results are compared with theoretical and experimental data from literature and calculated cross sections...

  15. Van der Waals coefficients for alkali metal clusters and their size dependence

    Indian Academy of Sciences (India)

    Arup Banerjee; Manoj K Harbola

    2006-02-01

    In this paper we employ the hydrodynamic formulation of time-dependent density functional theory to obtain the van der Waals coefficients 6 and 8 of alkali metal clusters of various sizes including very large clusters. Such calculations become computationally very demanding in the orbital-based Kohn-Sham formalism, but are quite simple in the hydrodynamic approach. We show that for interactions between the clusters of the same sizes, 6 and 8 scale as the sixth and the eighth power of the cluster radius, respectively, and approach their classically predicted values for the large size clusters.

  16. Shortcuts for understanding rovibronic spectroscopy of ultracold alkali metal diatomic molecules

    Science.gov (United States)

    Stwalley, William C.; Bellos, Michael; Carollo, Ryan; Banerjee, Jayita; Bermudez, Matthew

    2012-08-01

    The high-resolution rovibronic spectroscopies of cold and ultracold molecules (e.g. supersonic molecular beam excitation spectra (MB), photoassociation spectra of ultracold atoms (PA), resonance-enhanced multiphoton ionization spectra (REMPI), stimulated Raman transfer (SRT) spectra) are of major current interest. This manuscript summarizes the significant level of understanding of these various spectroscopies, enabled by using simple graphical and semiclassical ideas and shortcuts. Physical realizations of these spectroscopies will be illustrated using the alkali metal diatomic molecules, both homonuclear (e.g. Rb2) and heteronuclear (e.g. KRb).

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

    Science.gov (United States)

    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.

  18. Characterization of alkali-metal and alkaline-earth nitrates by vibrational spectroscopy

    Directory of Open Access Journals (Sweden)

    Martínez, S.

    1992-09-01

    Full Text Available Infrared spectra of sodium and potassium alkaline-metal nitrates and magnesium and calcium alkali-earth nitrates in solid phase had been recorded in order to assign the fundamental bands. The influence of the dispersal médium (alkaline halide, employed in the solid sample preparation have been discussed. The quantitative measurements of the band in ten sities at 1387 cm-1 (present in the I.R. spectra of the four nitrates in KBr médium allowed us to determine the Lambert-Beer law slopes for each compound. These values are differents (bearing in mind experimental random errors, so we have could to affirm the nonexistence of solid solution between the nitrate and the alkaline halide médium. The L-B law obtained by us can be used for the Identification differentiation and quantitative analysis of these nitrates in solid phase, even if they are present in a very low concentration.

    Se ha realizado la asignación de los espectros infrarrojo (IR de los nitratos alcalinos, sódico y potásico, y de los alcalinotérreos, magnésico y cálcico, en estado sólido. Se ha visto la influencia del medio dispersante (haluro alcalino, utilizado en la preparación de la muestra sólida. El estudio cuantitativo de la absorbencia de la banda a 1.387 cm-1 (presente en los espectros IR de los cuatro nitratos en medio KBr permite determinar las pendientes de la Ley de Lambert-Beer Se comprueba que dichas pendientes son diferentes lo que conduce a poder afirmar que no se produce disolución sólida entre el KBr y el nitrato alcalino o alcalinotérreo. La determinación de la ley de Lambert-Beer permite la identificación y el análisis cualitativo y cuantitativo por espectroscopia IR de estos nitratos cuando están presentes en bajas concentraciones en muestras sólidas.

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

    Science.gov (United States)

    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

  20. IDENTIFICATION OF PHASE COMPOSITION OF BINDERS FROM ALKALI-ACTIVATED MIXTURES OF GRANULATED BLAST FURNACE SLAG AND FLY ASH

    Directory of Open Access Journals (Sweden)

    JOZEF VLČEK

    2014-03-01

    Full Text Available The prepared alkali-activated binders (AAB and composites using suitable latent hydraulic raw materials represent an alternative to materials based on Portland cements. This paper deals with ways how to influence the functional parameters of AAB by setting up mixtures of granulated blast furnace slag (GBFS and fly ash with selected chemical compositions. In this way the course of hydration process is modified and the phase composition of products of alkali activation is changed as well as their final properties. The amorphous character of the hydration products makes evaluation of the phase composition of hardened AAB difficult and significantly limits the number of experimental techniques suitable to characterise their phase composition. It was observed that measuring the pH of water extracts obtained from the alkali-activated mixtures can give supplementary information about the process of hardening of alkali-activated mixtures of GBFS and fly ash.

  1. Alkali metal-cationized serine clusters studied by sonic spray ionization tandem mass spectrometry.

    Science.gov (United States)

    Nanita, Sergio C; Sokol, Ewa; Cooks, R Graham

    2007-05-01

    Serine solutions containing salts of alkali metals yield magic number clusters of the type (Ser(4)+C)(+), (Ser(8)+C)(+), (Ser(12)+C)(+), and (Ser(17)+2C)(+2) (where C = Li(+), Na(+), K(+), Rb(+), or Cs(+)), in relative abundances which are strongly dependent on the cation size. Strong selectivity for homochirality is involved in the formation of serine tetramers cationized by K(+), Rb(+), and Cs(+). This is also the case for the octamers cationized by the smaller alkalis but there is a strong preference for heterochirality in the octamers cationized by the larger alkali cations. Tandem mass spectrometry shows that the octamers and dodecamers cationized by K(+), Rb(+), and Cs(+) dissociate mainly by the loss of Ser(4) units, suggesting that the neutral tetramers are the stable building blocks of the observed larger aggregates, (Ser(8)+C)(+) and (Ser(12)+C)(+). Remarkably, although the Ser(4) units are formed with a strong preference for homochirality, they aggregate further regardless of their handedness and, therefore, with a preference for the nominally racemic 4D:4L structure and an overall strong heterochiral preference. The octamers cationized by K(+), Rb(+), or Cs(+) therefore represent a new type of cluster ion that is homochiral in its internal subunits, which then assemble in a random fashion to form octamers. We tentatively interpret the homochirality of these tetramers as a consequence of assembly of the serine molecules around a central metal ion. The data provide additional evidence that the neutral serine octamer is homochiral and is readily cationized by smaller ions.

  2. New bonding configuration on Si(111) and Ge(111) surfaces induced by the adsorption of alkali metals

    DEFF Research Database (Denmark)

    Lottermoser, L.; Landemark, E.; Smilgies, D.M.;

    1998-01-01

    The structure of the (3×1) reconstructions of the Si(111) and Ge(111) surfaces induced by adsorption of alkali metals has been determined on the basis of surface x-ray diffraction and low-energy electron diffraction measurements and density functional theory. The (3×1) surface results primarily f...... from the substrate reconstruction and shows a new bonding configuration consisting of consecutive fivefold and sixfold Si (Ge) rings in 〈11̅ 0〉 projection separated by channels containing the alkali metal atoms. © 1998 The American Physical Society......The structure of the (3×1) reconstructions of the Si(111) and Ge(111) surfaces induced by adsorption of alkali metals has been determined on the basis of surface x-ray diffraction and low-energy electron diffraction measurements and density functional theory. The (3×1) surface results primarily...

  3. Direct surface charging and alkali-metal doping for tuning the interlayer magnetic order in planar nanostructures

    Science.gov (United States)

    Dasa, Tamene R.; Stepanyuk, Valeri S.

    2015-08-01

    The continuous reduction of magnetic units to ultrasmall length scales inspires efforts to look for a suitable means of controlling magnetic states. In this study, we show two surface charge alteration techniques for tuning the interlayer exchange coupling of ferromagnetic layers separated by paramagnetic spacers. Our ab initio study reveals that already a modest amount of extra charge can switch the mutual alignment of the magnetization from antiferromagnetic to ferromagnetic or vice versa. We also propose adsorption of alkali metals as an alternative way of varying the electronic and chemical properties of magnetic surfaces. Clear evidence is found that the interlayer magnetic order can be reversed by adsorbing alkali metals on the magnetic layer. Moreover, alkali-metal overlayers strongly enhance the perpendicular magnetic anisotropy in FePt thin films. These findings combined with atomistic spin model calculations suggest that the electronic or ionic way of surface charging can have a crucial role for magnetic hardening and spin state control.

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

    Science.gov (United States)

    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.

  5. Metal-mediated aminocatalysis provides mild conditions: Enantioselective Michael addition mediated by primary amino catalysts and alkali-metal ions

    Directory of Open Access Journals (Sweden)

    Matthias Leven

    2013-01-01

    Full Text Available Four catalysts based on new amides of chiral 1,2-diamines and 2-sulfobenzoic acid have been developed. The alkali-metal salts of these betaine-like amides are able to form imines with enones, which are activated by Lewis acid interaction for nucleophilic attack by 4-hydroxycoumarin. The addition of 4-hydroxycoumarin to enones gives ee’s up to 83% and almost quantitative yields in many cases. This novel type of catalysis provides an effective alternative to conventional primary amino catalysis were strong acid additives are essential components.

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

    Science.gov (United States)

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

    2014-12-03

    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.

  7. Enthalpic Interaction for α-Amino Acid with Alkali Metal Halides in Water

    Institute of Scientific and Technical Information of China (English)

    LU,Yan(卢雁)

    2004-01-01

    The studies of the enthalpic interaction parameters, hxy, hxyy and hxxv, of alkali metal halides with glycine,α-alanine and α-aminobutyric acid were published. Synthetic considering of the results of the studies, some interesting behaviors of the interaction between alkali metal halides and the α-amino acids have been found. The values of hxy will increase with the increase of the number of carbon atoms in alkyl side chain of amino acid molecules and decrease with the increase of the radius of the ions. The increasing of the salt's effect on the hydrophobic hydration structure as the radii of anion is more obvious than as that of cation. The value of hxxy will regularly decrease with the increase of the number of carbon atoms in the alkyl chain of amino acids and linear increase with the increase of the radius. But the relation of hxxy with the radius of cations is not evident. The value of hxyy will increase with the increase of the radii of the ions. As the increase of the number of carbon atoms of amino acids, hxyy is decreas for the ions which have lager size and there is a maximum value at α-alanine for the ions which have small size. The behaviors of the interaction mentioned above were further discussed in view of electrostatic and structural interactions.

  8. 3718-F Alkali Metal Treatment and Storage Facility Closure Plan. Revision 1

    Energy Technology Data Exchange (ETDEWEB)

    None

    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.

  9. Challenges and Prospect of Non-aqueous Non-alkali (NANA) Metal-Air Batteries.

    Science.gov (United States)

    Gelman, Danny; Shvartsev, Boris; Ein-Eli, Yair

    2016-12-01

    Non-aqueous non-alkali (NANA) metal-air battery technologies promise to provide electrochemical energy storage with the highest specific energy density. Metal-air battery technology is particularly advantageous being implemented in long-range electric vehicles. Up to now, almost all the efforts in the field are focused on Li-air cells, but other NANA metal-air battery technologies emerge. The major concern, which the research community should be dealing with, is the limited and rather poor rechargeability of these systems. The challenges we are covering in this review are related to the initial limited discharge capacities and cell performances. By comprehensively reviewing the studies conducted so far, we show that the implementation of advanced materials is a promising approach to increase metal-air performance and, particularly, metal surface activation as a prime achievement leading to respectful discharge currents. In this review, we address the most critical areas that need careful research attention in order to achieve progress in the understanding of the physical and electrochemical processes in non-aqueous electrolytes applied in beyond lithium and zinc air generation of metal-air battery systems.

  10. Researches of the electrotechnical laboratory. No. 973: Study on alkali metal thermoelectric converter

    Science.gov (United States)

    Tanaka, K.; Negishi, A.; Honda, T.; Fujii, T.; Masuda, T.; Nozaki, K.

    1995-03-01

    The alkali metal thermoelectric converter (AMTEC) utilizing the sodium ion conducting Beta' '- alumina solid electrolyte (BASE) is a device to convert heat energy to electric energy directly. It is characterized by high conversion efficiencies (20 to 40 percent), high power densities (1 W/sq cm), no moving parts, low maintenance requirements, high durability, and efficiency independent of size. Because of these merits, AMTEC is one of the most promising candidate for dispersed small scale power station, remote power station and aerospace power systems. In this paper, the theoretical and experimental studies on the thin film electrodes characteristics, power generating characteristics, cell efficiency, integral electrode with large current lead, porous metal current lead, series connected cells power generation, potassium AMTEC, wick return AMTEC and system analysis for space and grand use are reported.

  11. Hydrothermal synthesis of mixed rare earth-alkali metal or ammonium fluorides

    Institute of Scientific and Technical Information of China (English)

    由芳田; 黄世华; 时秋峰

    2010-01-01

    The recent results on hydrothermal synthesis of mixed rare earth-alkali or ammonium fluorides were presented. The initial ratios of the starting materials, pH value and reaction temperature were the critical factors for obtaining the single-phase product. Four main types of complex rare earth fluorides, AREF4, A2REF5, ARE2F7 and ARE3F10 (A=Na+, K+, Rb+, NH4+), appeared in the primary hydrothermal reactions. The correlation between cation sizes and the formation of mixed rare earth fluorides under mild hydro...

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  14. Effect of Alkali Ions on the Amorphous to Crystalline Phase Transition of Silica

    Science.gov (United States)

    Venezia, A. M.; La Parola, V.; Longo, A.; Martorana, A.

    2001-11-01

    The effect of the addition of alkali ions to commercial amorphous silica, generally used as support for heterogeneous catalysts, has been investigated from the point of view of morphological and structural changes. Samples of alkali-doped silica were prepared by impregnation and subsequent calcination at various temperatures. The structural effect of Li, Na, K, and Cs was determined by use of techniques such as wide-angle (WAXS) and small-angle X-ray scattering (SAXS). The WAXS diffractograms, analyzed with the Rietveld method using the GSAS program, allowed qualitative and quantitative identification of the fraction of the different silica polymorphs like quartz, tridymite, and cristobalite. SAXS measurements, using the classical method based on Porod's law, yielded the total surface area of the systems. The calculated areas were compared with the surface areas determined by the nitrogen adsorption technique using the analytical method of Brunauer-Emmett-Teller. The results are explained in terms of sizes of the alkali ions and cell volume of the different crystalline phases.

  15. Nature of the Charge Localized Between Alkali Adatoms and Metal Substrates

    OpenAIRE

    Wertheim, G. K.; Riffe, D. Mark; Citrin, P. H.

    1994-01-01

    Two previously unappreciated features in photoemission spectra from alkali atoms adsorbed on W(110), namely, the sign of the alkali-induced surface-atom core-level shift of the substrate at low coverage and the very large alkali shallow core-hole lifetime width at all coverages, show that the alkali-substrate interaction is not well described by a transfer of alkali charge. Instead, both features point to the formation of a charge cloud between the alkali adatom and substrate that is d...

  16. Investigation of anti-Relaxation coatings for alkali-metal vapor cells using surface science techniques

    Energy Technology Data Exchange (ETDEWEB)

    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. Alkali metal salts of formazanate ligands : diverse coordination modes as a result of the nitrogen-rich [NNCNN] ligand backbone

    NARCIS (Netherlands)

    Travieso-Puente, Raquel; Chang, Mu-Chieh; Otten, Edwin

    2014-01-01

    Alkali metal salts of redox-active formazanate ligands were prepared, and their structures in the solid-state and in solution are determined. The nitrogen-rich [NNCNN] backbone of formazanates results in a varied coordination chemistry, with both the internal and terminal nitrogen atoms available fo

  18. Crown-Ether Derived Graphene Hybrid Composite for Membrane-Free Potentiometric Sensing of Alkali Metal Ions

    DEFF Research Database (Denmark)

    Olsen, Gunnar; Ulstrup, Jens; Chi, Qijin

    2016-01-01

    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...

  19. Synthesis and Selective Coloration of Monoaza Crown Ethers Bearing Picrylamino-type Side Arms for Alkali Metal Salts and Methylamine

    Institute of Scientific and Technical Information of China (English)

    Wei ZENG; Zhi Hua MAO; Mi GONG; Chun Chun ZHANG; Sheng Ying QIN; Jun SU

    2003-01-01

    N-pivot lariat ethers with picrylamino group as a chromophore (1, 2 and 3) have been prepared by reaction of N-(4-aminoaryl)monoaza crown ethers with picryl chrolide, and the selective coloration of 1, 2 and 3 for alkali metal salts and amines has been studied by UV-Vis spectra.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2005-10-31

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

  1. Difference of coordination between alkali- and alkaline-earth-metal ions to a symmetrical α,α',δ,δ'-tetramethylcucurbit[6]uril.

    Science.gov (United States)

    Chen, Wen-Jian; Yu, Da-Hai; Xiao, Xin; Zhang, Yun-Qian; Zhu, Qian-Jiang; Xue, Sai-Feng; Tao, Zhu; Wei, Gang

    2011-08-01

    To explore differences in coordination between alkali- and alkaline-earth-metal ions and cucurbit[n]urils, a water-soluble α,α',δ,δ'-tetramethylcucurbit[6]uril (TMeQ[6]) was used to synthesize a series of complexes and their supramolecular assemblies, based on the coordination of TMeQ[6] with alkali- and alkaline-earth-metal ions. The complexes and corresponding supramolecular assemblies were structurally characterized by single-crystal X-ray diffraction. Unlike cucurbituril (Q[6]), which formed the metal-Q[6] polymers based on the direct coordination of carbonyl oxygen atoms to the alkali-metal ions, TMeQ[6] formed metal-TMeQ[6] polymers based on the direct coordination of carbonyl oxygen atoms with the alkaline-earth-metal ions rather than the alkali-metal ions.

  2. Magnetism in alkali-metal-doped wurtzite semiconductor materials controlled by strain engineering

    Science.gov (United States)

    Guo, J. H.; Li, T. H.; Liu, L. Z.; Hu, F. R.

    2016-09-01

    The study of the magnetism and optical properties of semiconductor materials by defect engineering has attracted much attention because of their potential uses in spintronic and optoelectronic devices. In this paper, first-principle calculations discloses that cationic vacancy formation energy of the doped wurtzite materials can be sharply decreased due to alkali metal dopants and shows that their magnetic properties strongly depend on defect and doping concentration. This effect can be ascribed to the volume change induced by foreign elements doped into the host system and atomic population's difference. The symmetric deformation induced by biaxial strain can further regulate this behavior. Our results suggest that the formation of cationic vacancy can be tailored by strain engineering and dopants incorporation.

  3. Separation of hafnium from zirconium in their tetrachloride solution in molten alkali metal chlorides

    Energy Technology Data Exchange (ETDEWEB)

    Salyulev, A.B.; Kudyakov, V.Ya.; Smirnov, M.V.; Moskalenko, N.I. (AN SSSR, Sverdlovsk. Inst. Ehlektrokhimii)

    1984-08-01

    The coefficient of HfCl/sub 4/ and ZrCl/sub 4/ separation in the process of vapour sublimation from their solutions in molten NaCl, KCl, CsCl, NaCl-KCl and NaCl-CsCl equimolar mixtures is found to vary in the series from approximately 1.10 to approximately 1.22 and practically not to depend on the temperature (in the 600-910 deg) range and concentration (2-25 mol.% ZrCl/sub 4/+HfCl/sub 4/). HfCl/sub 4/ and ZrCl/sub 4/ are shown to form almost perfect solutions with each other, which in their turn form imperfect solutions with molten alkali metal chlorides, with the strength of hafnium complex chloride anions increasing higher than that of zirconium in the series from NaCl to CsCl.

  4. Alkali-metal electron spin density shift induced by a helium nanodroplet

    Science.gov (United States)

    Koch, Markus; Callegari, Carlo; Ernst, Wolfgang E.

    2010-04-01

    Helium (He) nanodroplets provide a cold and virtually unperturbing environment for the study of weakly bound molecules and van der Waals aggregates. High resolution microwave spectroscopy and the detection of electron spin transitions in doped He droplets have recently become possible. Measurements of hyperfine-resolved electron spin resonance in potassium (39K) and rubidium (85Rb) atoms on the surface of He droplets show small line shifts relative to the bare atoms. These shifts were recorded for all 2I + 1 components (I is the nuclear spin) of a transition at high accuracy for He droplets ranging in size from 1000 to 15,000 He atoms. Evaluation of the spectra yields the influence of the He environment on the electron spin density at the alkali-metal nucleus. A semi-empirical model is presented that shows good qualitative agreement with the measured droplet size dependent increase of Fermi contact interaction at the nuclei of dopant K and Rb.

  5. Structural systematic and crystal chemistry of novel borates with REE, Pb, Sr, and alkali metals

    Energy Technology Data Exchange (ETDEWEB)

    Belokoneva, E.L. [Moscow State Univ., Moscow (Russian Federation). Dept. of Crystallography and Crystal Chemistry

    2013-11-01

    Crystal structures of novel borates with REE, Pb, Sr and alkali metals were analyzed using classical fundamental buildings blocks approach. It is demonstrated that hexa-, penta-, tetra-, tri- and diborates subdivisions in systematic are real families of structures with the common peculiarities. According to the symmetrical way and the degree of FBB condensation structural-generic rows exist in every of subdivisions. Mega- or polyborates subdivision is valid for the structures with the different types of simplest FBB. In all new complex borates it is possible to separate FBB of equal or different types which are presented in isolated form or are connected into chains, layers or frameworks, and to find unexpected correlation between structures. The possibility to recognize and to visualize in this approach the polarity or non-polarity of the structural units and correspondingly the polarity or nonpolarity of the structures in the whole is very important for the conclusion on structure-properties relation. (orig.)

  6. An analytical model of Faraday rotation in hot alkali metal vapours

    CERN Document Server

    Kemp, Stefan L; Cornish, Simon L

    2011-01-01

    We report a thorough investigation into the absorptive and dispersive properties of hot caesium vapour, culminating in the development of a simple analytical model for off-resonant Faraday rotation. The model, applicable to all hot alkali metal vapours, is seen to predict the rotation observed in caesium, at temperatures as high as 115 $^{\\circ}$C, to within 1% accuracy for probe light detuned by greater than 2 GHz from the $D_{2}$ lines. We also demonstrate the existence of a weak probe intensity limit, below which the effect of hyperfine pumping is negligible. Following the identification of this regime we validate a more comprehensive model for the absorption and dispersion in the vicinity of the $D_{2}$ lines, implemented in the form of a computer code. We demonstrate the ability of this model to predict Doppler-broadened spectra to within 0.5% rms deviation for temperatures up to 50 $^{\\circ}$C.

  7. Momentum densities and Compton profiles of alkali-metal atoms

    Indian Academy of Sciences (India)

    Pranab Sarkar; Anupam Sarkar; S N Roy; B Talukdar

    2003-03-01

    It is assumed that the dynamics of valence electrons of alkali-metal atoms can be well accounted for by a quantum-defect theoretic model while the core electrons may be supposed to move in a self-consistent field. This model is used to study the momentum properties of atoms from 3Li to 37Rb. The numerical results obtained for the momentum density, moments of momentum density and Compton profile are found to be in good agreement with the results of more detailed configuration-interaction calculations for the atom 3Li. Similar results for 11Na, 19K and 37Rb are compared with the corresponding Hartree–Fock–Roothaan values only, for want of data from other realistic calculations.

  8. Alkali metal compatibility testing of candidate heater head materials for a Stirling engine heat transport system

    Science.gov (United States)

    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.

  9. Tris-[8]annulenyl Isocyanurate Trianion Triradical and Hexa-anion from the Alkali Metal Reduction of [8]Annulenyl Isocyanate.

    Science.gov (United States)

    Peters, Steven J; Klen, Joseph R

    2015-06-05

    The solution phase alkali metal reduction of [8]annulenyl isocyanate (C8H7NCO) yields an EPR spectrum, which reveals electron couplings to seven protons and only one nitrogen. Although this strongly suggested that the C8H7NCO anion radical was generated, experiments on the oxidized product reveal the actual reduced species to be tris-[8]annulenyl isocyanurate. Unlike the previously studied phenyl isocyanurate anion radical, the unpaired electron(s) is now localized within an [8]annulenyl moiety. Further exposure to metal results in the formation of an equilibrium mixture of trianion triradical and trianion radical species. The cyclotrimerization to form the isocyanurate is proposed to be driven by a reactive C8H7NCO dianion, which is produced from the large equilibrium disproportionation of the anion radical. Exhaustive reduction of the tris-[8]annulenyl isocyanurate with potassium in THF generates the first-ever observed hexa-anion of an isocyanurate. NMR analysis reveals that the polarity of the carbonyl bonds within this hexa-anion is augmented and is caused by the close proximity of K(+) ions, which are tightly ion paired to the three [8]annulenyl dianion rings. These preliminary studies on the reduction of C8H7NCO suggest that polymeric materials (e.g., polyisocyanates) made from this isocyanate might exhibit unique properties.

  10. Fast ionic conduction in tetravalent metal pyrophosphate-alkali carbonate composites: New potential electrolytes for intermediate-temperature fuel cells

    Science.gov (United States)

    Singh, Bhupendra; Bhardwaj, Aman; Gautam, Sandeep K.; Kumar, Devendra; Parkash, Om; Kim, In-Ho; Song, Sun-Ju

    2017-03-01

    Here we present a report on synthesis and characterization of tetravalent metal pyrophosphate (TMP) and alkali carbonate (A2CO3; A = Li and/or Na) composites. The TMP-carbonate composites are prepared by mixing indium-doped tin pyrophosphate or yttrium-doped zirconium pyrophosphate with Li2CO3 or an eutectic mixture of Li2CO3-Na2CO3 in different wt.% ratios. The phase composition, microstructure and electrical conductivity of the sintered specimen are analyzed. In addition, the effect of different TMP and A2CO3 phases is investigated. A maximum ionic conductivity of 5.5 × 10-2 S cm-1 at 630 °C is observed in this study with a Sn0.9In0.1P2O7-Li2CO3 composite. Based on the literature data, TMP-carbonate composites can be considered to be primarily a proton and oxygen-ion co-ionic conductor and, therefore, have strong potential as electrolytes in fuel cells in 500-700 °C range.

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

    Science.gov (United States)

    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.

  12. UV-visible spectroscopic analysis of electrical properties in alkali metal-doped amorphous zinc tin oxide thin-film transistors.

    Science.gov (United States)

    Lim, Keon-Hee; Kim, Kyongjun; Kim, Seonjo; Park, Si Yun; Kim, Hyungjun; Kim, Youn Sang

    2013-06-04

    Solution-processed and alkali metals, such as Li and Na, are introduced in doped amorphous zinc tin oxide (ZTO) semiconductor TFTs, which show better electrical performance, such as improved field effect mobility, than intrinsic amorphous ZTO semiconductor TFTs. Furthermore, by using spectroscopic UV-visible analysis we propose a comprehensive technique for monitoring the improved electrical performance induced by alkali metal doping in terms of the change in optical properties. The change in the optical bandgap supported by the Burstein-Moss theory could successfully show a mobility increase that is related to interstitial doping of alkali metal in ZTO semiconductors.

  13. Room temperature inorganic ``quasi-molten salts`` as alkali-metal electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Xu, K.; Zhang, S.; Angell, C.A. [Arizona State Univ., Tempe, AZ (United States). Dept. of Chemistry

    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.

  14. Alkali metal pool boiler life tests for a 25 kWe advanced Stirling conversion system

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

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

  16. Energetics and bonding in aluminosilicate rings with alkali metal and alkaline-earth metal charge-compensating cations.

    Science.gov (United States)

    Gatti, Carlo; Ottonello, Giulio; Richet, Pascal

    2012-08-23

    The stabilizing effect of alkali and alkaline-earth metal ions on the oxygen donors of four- and six-membered faujausite-like rings has been calculated in terms of Kohn-Sham core-level (O1s) energy shifts with respect to these same complexes without cations. The results confirm and complement earlier investigations by Vayssilov and co-workers where Na(+) and K(+) were the only complexing cations. The oxygen donor centers in six-membered rings are stabilized by -3.6 ± 0.4, -3.9 ± 0.5, -7.3 ± 0.1, and -7.6 ± 0.2 eV by K(+), Na(+), Ca(2+), and Mg(2+) adions, respectively. The energy shifts are even greater for four-membered rings where the stabilization effects attain -3.7 ± 0.1, -4.1 ± 0.1, -8.1 ± 0.1, and -9.0 ± 0.1 eV, respectively. These effects are also observed on the low-lying σ-bonding and antibonding molecular orbitals (MOs) of the oxygen framework, but in a less systematic fashion. Clear relationships with the core-level shifts are found when the effects of alkali metal complexation are evaluated through electron localization/delocalization indices, which are defined in terms of the whole wave function and not just of the individual orbitals. Complexation with cations not only involves a small but significant electron sharing of the cation with the oxygen atoms in the ring but also enhances electron exchange among oxygen atoms while reducing that between the O atoms and the Si or Al atoms bonded to them. Such changes slightly increase from Na to K and from Mg to Ca, whereas they are significantly enhanced for alkaline-earth metals relative to alkali metals. With respect to Al-free complexes, Si/Al substitution and cation charge compensation generally enhance electron delocalization among the O atoms, except between those that are linked through an Al atom, and cause either an increased or a decreased Si-O ionicity (smaller/higher electron exchange) depending on the position of O in the chain relative to the Al atom(s). The generally increased

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

    Science.gov (United States)

    Islam, Nasarul; Chimni, Swapandeep Singh

    2017-02-01

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

  18. The effect of alkali metals on combustion and pyrolysis of Lolium and Festuca grasses, switchgrass and willow

    Energy Technology Data Exchange (ETDEWEB)

    R. Fahmi; A.V. Bridgwater; L.I. Darvell; J.M. Jones; N. Yates; S. Thain; I.S. Donnison [Aston University, Birmingham (United Kingdom). Bio-Energy Research Group, Chemical Engineering and Applied Chemistry

    2007-07-15

    The effect of alkali metals on the thermal degradation of biomass during combustion and pyrolysis has been investigated for 19 Lolium and Festuca grass varieties. These samples have been grown under the same conditions, but has been genetically mutated to give varying lignin contents in the range 2-6% measured by Klason. These grasses also have a high alkali metal content resulting in a high ash content. In order to compare the Lolium and Festuca grasses willow chip and switchgrass were also studied to act as a reference fuels. All samples were subjected to different washing conditions to investigate the effect of decreasing the metal content. The resulting biomass samples were studied for pyrolysis characteristics using thermogravimetric analysis (TGA) and pyrolysis gas chromatography-mass spectrometry (pyroprobe-GC/MS) and for combustion characteristics by TGA. A strong catalytic effect of metals, particularly potassium, was observed in both pyrolysis and combustion. Also, it was found that as the lignin content increases, the metal content (especially potassium and sodium) decreases. Furthermore, the char yield from pyrolysis (measured at 773 K from TGA pyrolysis traces) increases as metals increase, and hence char yield increases as the lignin content decreases. Py-GCMS showed that peak intensities varied for untreated and treated samples; in particular the levoglucosan yield is higher and the hydroxyacetaldehyde yield is lower for treated (low metal content) samples. This supports previous work mechanisms by Liden et al. in which alkali metals promote an ionic route that favours ring-scission and hydroxyacetaldehyde formation. 13 refs., 10 figs., 4 tabs.

  19. Shifts in the ESR spectra of alkali-metal atoms (Li, Na, K, Rb) on helium nanodroplets.

    Science.gov (United States)

    Hauser, Andreas W; Gruber, Thomas; Filatov, Michael; Ernst, Wolfgang E

    2013-03-18

    He-droplet-induced changes of the hyperfine structure constants of alkali-metal atoms are investigated by a combination of relativistically corrected ab initio methods with a simulation of the helium density distribution based on He density functional theory. Starting from an accurate description of the variation of the hyperfine structure constant in the M-He diatomic systems (M=Li, Na, K, Rb) as a function of the interatomic distance we simulate the shifts induced by droplets of up to 10,000 (4)He atoms. All theoretical predictions for the relative shifts in the isotropic hyperfine coupling constants of the alkali-metal atoms attached to helium droplets of different size are then tied to a single, experimentally derived parameter of Rb.

  20. Characterization of Adsorbed Alkali Metal Ions in 2:1 Type Clay Minerals from First-Principles Metadynamics.

    Science.gov (United States)

    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.

  1. Ab initio quantum Monte Carlo study of the binding of a positron to alkali-metal hydrides.

    Science.gov (United States)

    Kita, Yukiumi; Maezono, Ryo; Tachikawa, Masanori; Towler, Mike D; Needs, Richard J

    2011-08-07

    Quantum Monte Carlo methods are used to investigate the binding of a positron to the alkali-metal hydrides, XH (X = Na and K). We obtain positron affinities for the NaH and KH molecules of 1.422(10) eV and 2.051(39) eV, respectively. These are considerably larger than the previous results of 1.035 eV and 1.273 eV obtained from multireference single- and double-excitation configuration interaction calculations. Together with our previous results for [LiH;e(+)] [Y. Kita et al., J. Chem. Phys. 131, 134310 (2009)], our study confirms the strong correlation between the positron affinity and dipole moment of alkali-metal hydrides.

  2. The relationship between molecular structure and biological activity of alkali metal salts of vanillic acid: Spectroscopic, theoretical and microbiological studies

    Science.gov (United States)

    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.

  3. Optical detection of sodium salts of fluoride, acetate and phosphate by a diacylhydrazine ligand by the formation of a colour alkali metal complex

    Indian Academy of Sciences (India)

    Purnandhu Bose; Ranjan Dutta; I Ravikumar; Pradyut Ghosh

    2011-11-01

    A solution of N, N'-diacylhydrazine ligand in organic solvent is potential for colourimetric detection of F−/AcO−/PO$^{3−}_{4}$ via -NH deprotonation, tautomerization and its stabilization as a colour alkali metal complex.

  4. Research Investigation Directed Toward Extending the Useful Range of the Electromagnetic Spectrum. [atomic spectra and electronic structure of alkali metals

    Science.gov (United States)

    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.

  5. Alkali Metal Ion Complexes with Phosphates, Nucleotides, Amino Acids, and Related Ligands of Biological Relevance. Their Properties in Solution.

    Science.gov (United States)

    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  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).

  6. Collisions of alkali-metal atoms Cs and Rb in the ground state. Spin exchange cross sections

    Science.gov (United States)

    Kartoshkin, V. A.

    2016-09-01

    Collisions of alkali-metal atoms 133Cs and 85Rb in the ground state are considered in the energy interval of 10-4-10-2 au. Complex cross sections of the spin exchange, which allow one to calculate the processes of polarization transfer and the relaxation times, as well as the magnetic resonance frequency shifts caused by spin exchange Cs-Rb collisions, are obtained.

  7. An Alkali-Vapor Cell with Metal Coated Windows for Efficient Application of an Electric Field

    CERN Document Server

    Sarkisyan, D; Guena, J; Lintz, M; Bouchiat, M A; Sarkisyan, David; Gu\\'{e}na, Jocelyne; Lintz, Michel; Bouchiat, Marie-Anne

    2005-01-01

    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 2 kV/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 ...

  8. Alkali-vapor cell with metal coated windows for efficient application of an electric field

    Science.gov (United States)

    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.

  9. Faraday effect in alkali-metal vapors in a strong bichromatic field of laser light

    Science.gov (United States)

    Karagodova, T. Ya.; Kuptsova, A. V.

    2002-04-01

    Results of a numerical study of the Faraday effect arising upon propagation of the light beams with the frequencies ω L1 (resonant to the nS 1/2- nP 1/2, 3/2 transitions) and ω L2 (resonant to the nP 1/2, 3/2-( n+2) S 1/2 transitions) through alkali-metal vapors are presented. Characteristics of the magneto-optical rotation spectra at each of the frequencies are strongly affected by the second intense radiation field resonant to the adjacent transition. When the atoms interact with two strong light waves, resonant to adjacent transitions, and with a magnetic field, the shape of the Faraday rotation spectra depends on the energy shifts of the atomic states that arise due to the dynamic Stark effect and the Zeeman effect (the Paschen-Back or an intermediate-type effect), as well as due to the difference of populations of these states caused by the interaction of the atoms with the fields. The results obtained show that in the frequency selection method, based on the resonance Faraday effect, the frequency of the generated narrow-band beam can be tuned by the intensity of the strong wave, resonant to the transition between the excited states.

  10. Universal ultracold collision rates for polar molecules of two alkali-metal atoms.

    Science.gov (United States)

    Julienne, Paul S; Hanna, Thomas M; Idziaszek, Zbigniew

    2011-11-14

    Universal collision rate constants are calculated for ultracold collisions of two like bosonic or fermionic heteronuclear alkali-metal dimers involving the species Li, Na, K, Rb, or Cs. Universal collisions are those for which the short range probability of a reactive or quenching collision is unity such that a collision removes a pair of molecules from the sample. In this case, the collision rates are determined by universal quantum dynamics at very long range compared to the chemical bond length. We calculate the universal rate constants for reaction of the reactive dimers in their ground vibrational state v = 0 and for vibrational quenching of non-reactive dimers with v ≥ 1. Using the known dipole moments and estimated van der Waals coefficients of each species, we calculate electric field dependent loss rate constants for collisions of molecules tightly confined to quasi-two-dimensional geometry by a one-dimensional optical lattice. A simple scaling relation of the quasi-two-dimensional loss rate constants with dipole strength, trap frequency and collision energy is given for like bosons or like fermions. It should be possible to stabilize ultracold dimers of any of these species against destructive collisions by confining them in a lattice and orienting them with an electric field of less than 20 kV cm(-1).

  11. Exchange-correlation interaction and AO-hybridization of alkali-metal atomic clusters.

    Science.gov (United States)

    Liu, Xuan; Ito, Haruhiko; Torikai, Eiko

    2013-09-19

    The structure of alkali-metal atomic clusters is optimized with B3P86 hybrid functional for the highest spin state as well as with B3LYP hybrid functional for the lowest spin state. A dramatic change from plane to solid occurs in the highest spin state when the number of constituent atoms is four. The binding, exchange, and correlation energies are evaluated for both the highest and lowest spin states. Next, we explore the dependence of the exchange and correlation energies on the binding energy. The exchange energy contributes to the formation of the highest spin clusters, whereas the correlation energy contributes to the formation of the lowest spin clusters. The highest spin clusters are most stable when the exchange energy is a minimum. Then, to see why the ferromagnetic bond among spin-aligned identical atoms arises against Pauli exclusion principle, we estimate the mixing ratio of p orbitals in molecular orbitals. The s-p hybridization increases the binding energy in absolute value due to the extensive overlap of molecular orbitals and leads to generation of the highest spin clusters.

  12. Study of Spectral Character of Alkali Metals Using Microwave Plasma Torch Simultaneous Spectrometer

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    A microwave plasma torch(MPT) simultaneous spectrometer was used to study the spectral character and the matrix effect on alkali metal ions in solution. The main parameters were optimized. The microwave forward power was 100 W. The argon flow rate that was used to sustain the Ar-MPT included the flow rate of carrier gas and the flow rate of support gas, which were 0.8 and 1.0 L/min, respectively. The HCl concentration in the solution was 0.02 mol/L. The observation height was 9.0 mm. The detection limits of Li, Na, K, Rb, and Cs were 0.0003, 0.0004, 0.009, 0.07 and2.4 mg/L, respectively, and the results obtained by the Ar-MPT were compared with those obtained by argon inductively coupled plasma(Ar-ICP) and argon microwave induced plasma(Ar-MIP). The interference effects of several matrix elements were also studied.

  13. Recent Advances In Alkali Metal Thermoelectric Converter (AMTEC) Electrode Performance And Modeling

    Science.gov (United States)

    Bankston, C. P.; Williams, R. M.; Jeffries-Nakamura, B.; Loveland, M. E.; Underwood, M. L.; Cole, T.

    1988-04-01

    The Alkali Metal Thermoelectric Converter (AMTEC) is a direct energy conversion device, utilizing a high sodium vapor pressure or activity ratio across a beta"-alumina solid electrolyte (BASE). It has been operated at a device efficiency of 19% and at power densities near 1.0 W/cm2. This paper describes progress on the remaining scien-tific issue which must be resolved to demonstrate AMTEC feasibility for space power systems: a stable, high power density electrode. Two electrode systems have recently been discovered at JPL that now have the potential to meet space power requirements. One of these is a very thin sputtered molybdenum film, less than 0.5 micron thick, with over-lying current collection grids. This electrode has experimentally demonstrated stable performance at 0.4-0.5 W/cm2 for hundreds of hours. Recent modeling results show that at least 0.7 W/cm2 can be achieved. The model of electrode performance now includes all loss mechanisms, including charge transfer resistances at the electrode/electrolyte interface. A second electrode composition, co-sputtered platinum/tungsten, has demon-strated 0.8 W/cm2 for 160 hours. Systems studies show that a stable electrode performance of 0.6 W/cm2 will enable high efficiency (near 20%) space power systems.

  14. Quantum control of the hyperfine-coupled electron and nuclear spins in alkali-metal atoms

    Science.gov (United States)

    Merkel, Seth T.; Jessen, Poul S.; Deutsch, Ivan H.

    2008-08-01

    We study quantum control of the full hyperfine manifold in the ground-electronic state of alkali-metal atoms based on applied radio frequency and microwave fields. Such interactions should allow essentially decoherence-free dynamics and the application of techniques for robust control developed for NMR spectroscopy. We establish the conditions under which the system is controllable in the sense that one can generate an arbitrary unitary map on the system. We apply this to the case of Cs133 with its d=16 dimensional Hilbert space of magnetic sublevels in the 6S1/2 state, and design control wave forms that generate an arbitrary target state from an initial fiducial state. We develop a generalized Wigner function representation for this space consisting of the direct sum of two irreducible representations of SU(2), allowing us to visualize these states. The performance of different control scenarios is evaluated based on the ability to generate a high-fidelity operation in an allotted time with the available resources. We find good operating points commensurate with modest laboratory requirements.

  15. Silicon halide-alkali metal flames as a source of solar grade silicon

    Science.gov (United States)

    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.

  16. Atomic many-body effects and Lamb shifts in alkali metals

    Science.gov (United States)

    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.

  17. Alkali metal cation doped Al-SBA-15 for carbon dioxide adsorption.

    Science.gov (United States)

    Zukal, Arnošt; Mayerová, Jana; Čejka, Jiří

    2010-01-01

    Mesoporous aluminosilicate adsorbents for carbon dioxide were prepared by the grafting of aluminium into SBA-15 silica using an aqueous solution of aluminium chlorohydrate. As the ion exchange sites are primarily associated with the presence of tetrahedrally coordinated aluminium, extra-framework aluminium on the SBA-15 surface was inserted into the silica matrix by a treatment with an aqueous solution of NH(4)OH. Synthesized mesoporous aluminosilicate preserving all the characteristic features of a mesoporous molecular sieve was finally modified by the alkali metal cation exchange. To examine carbon dioxide adsorption on prepared materials, adsorption isotherms in the temperature range from 0 °C to 60 °C were measured. Based on the known temperature dependence of adsorption isotherms, isosteric adsorption heats giving information on the surface energetics of CO(2) adsorption were calculated and discussed. The comparison of carbon dioxide isotherms obtained on aluminosilicate SBA-15, aluminosilicate SBA-15 containing cations Na(+) and K(+) and activated alumina F-200 reveals that the doping with sodium or potassium cations dramatically enhances adsorption in the region of equilibrium pressures lower than 10 kPa. Therefore, synthesized aluminosilicate adsorbents doped with Na(+) or K(+) cations are suitable for carbon dioxide separation from dilute gas mixtures.

  18. Alkali metal salts of formazanate ligands: diverse coordination modes as a result of the nitrogen-rich [NNCNN] ligand backbone.

    Science.gov (United States)

    Travieso-Puente, Raquel; Chang, Mu-Chieh; Otten, Edwin

    2014-12-28

    Alkali metal salts of redox-active formazanate ligands were prepared, and their structures in the solid-state and in solution are determined. The nitrogen-rich [NNCNN] backbone of formazanates results in a varied coordination chemistry, with both the internal and terminal nitrogen atoms available for bonding with the alkali metal. The potassium salt K[PhNNC(p-tol)NNPh]·2THF (1-K) is dimeric in the solid state and even in THF solution, as a result of the K atom bridging via interaction with a terminal N atom and the aromatic ring of a second unit. Conversely, for the compounds Na[MesNNC(CN)NNMes]·2THF (2-Na) and Na[PhNNC((t)Bu)NNPh] (3-Na) polymeric and hexameric structures are found in the solid state respectively. The preference for binding the alkali metal through internal N atoms (1-K and 2-Na) to give a 4-membered chelate, or via internal/external N atoms (5-membered chelate in 3-Na), contrasts with the 6-membered chelate mode observed in our recently reported formazanate zinc complexes.

  19. UV and IR spectroscopy of cold 1,2-dimethoxybenzene complexes with alkali metal ions.

    Science.gov (United States)

    Inokuchi, Yoshiya; Boyarkin, Oleg V; Ebata, Takayuki; Rizzo, Thomas R

    2012-04-01

    We report UV photodissociation (UVPD) and IR-UV double-resonance spectra of 1,2-dimethoxybenzene (DMB) complexes with alkali metal ions, M(+)·DMB (M = Li, Na, K, Rb, and Cs), in a cold, 22-pole ion trap. The UVPD spectrum of the Li(+) complex shows a strong origin band. For the K(+)·DMB, Rb(+)·DMB, and Cs(+)·DMB complexes, the origin band is very weak and low-frequency progressions are much more extensive than that of the Li(+) ion. In the case of the Na(+)·DMB complex, spectral features are similar to those of the K(+), Rb(+), and Cs(+) complexes, but vibronic bands are not resolved. Geometry optimization with density functional theory indicates that the metal ions are bonded to the oxygen atoms in all the M(+)·DMB complexes. For the Li(+) complex in the S(0) state, the Li(+) ion is located in the same plane as the benzene ring, while the Na(+), K(+), Rb(+), and Cs(+) ions are located off the plane. In the S(1) state, the Li(+) complex has a structure similar to that in the S(0) state, providing the strong origin band in the UV spectrum. In contrast, the other complexes show a large structural change in the out-of-plane direction upon S(1)-S(0) excitation, which results in the extensive low-frequency progressions in the UVPD spectra. For the Na(+)·DMB complex, fast charge transfer occurs from Na(+) to DMB after the UV excitation, making the bandwidth of the UVPD spectrum much broader than that of the other complexes and producing the photofragment DMB(+) ion.

  20. Design and Test of Advanced Thermal Simulators for an Alkali Metal-Cooled Reactor Simulator

    Science.gov (United States)

    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.

  1. New class of scorpionate: tris(tetrazolyl)-iron complex and its different coordination modes for alkali metal ions.

    Science.gov (United States)

    Park, Ka Hyun; Lee, Kang Mun; Go, Min Jeong; Choi, Sung Ho; Park, Hyoung-Ryun; Kim, Youngjo; Lee, Junseong

    2014-08-18

    We report formation of a new metallascorpionate ligand, [FeL3](3-) (IPtz), containing a Fe core and three 5-(2-hydroxyphenyl)-1H-tetrazole (LH2) ligands. It features two different binding sites, oxygen and nitrogen triangles, which consist of three oxygen or nitrogen donors from tetrazole. The binding affinities of the complex for three alkali metal ions were studied using UV spectrophotometry titrations. All three alkali metal ions show high affinities and binding constants (>3 × 10(6) M(-1)), based on the 1:1 binding isotherms to IPtz. The coordination modes of the alkali metals and IPtz in the solid were studied using X-ray crystallography; two different electron-donor sites show different coordination numbers for Li(+), Na(+), and K(+) ions. The oxygen triangles have the κ(2) coordination mode with Li(+) and κ(3) coordination mode with Na(+) and K(+) ions, whereas the nitrogen triangles show κ(3) coordination with K(+) only. The different binding affinities of IPtz in the solid were manipulated using multiple metal precursors. A Fe-K-Zn trimetallic complex was constructed by assembly of an IPtz ligand, K, and Zn precursors and characterized using X-ray crystallography. Oxygen donors are coordinated with the K ion via the κ(3) coordination mode, and nitrogen donors are coordinated with Zn metal by κ(3) coordination. The solid-state structure was confirmed to be a honeycomb coordination polymer with a one-dimensional infinite metallic array, i.e., -(K-K-Fe-Zn-Fe-K)n-.

  2. Alkali metal non-stoichiometric effects in (K{sub 0.5}Na{sub 0.5})NbO{sub 3} based piezoelectric ceramics

    Energy Technology Data Exchange (ETDEWEB)

    Lee, S. C.; Yeo, H. G.; Cho, J. H.; Sung, Y. S.; Kim, M. H.; Song, T. K.; Kim, S. S. [Changwon National University, Changwon (Korea, Republic of); Choi, B. C. [Pukyung National University, Busan (Korea, Republic of); Choi, K. S. [Sunchon National University, Sunchon, Chonnam (Korea, Republic of)

    2010-01-15

    Alkali-metal-excess lead-free 0.93(K{sub 0.5}Na{sub 0.5}){sub (1+x)}NbO{sub 3}-0.07LiNbO{sub 3} (KNNL) piezoelectric ceramics were prepared by using a solid state reaction. The contents of both K and Na were simultaneously controlled to 4 mol% excess. From X-ray diffraction and temperature-dependent dielectric constant measurements, a polymorphic phase transition (PPT) between the tetragonal and orthorhombic phases was observed by changing the stoichiometry of x. With increasing (K+Na) content, the PPT temperature increased, but the Curie temperature decreased. The highest piezoelectric constant was 189 pC/N for x = 0.01, where the PPT temperature was around room temperature.

  3. Modulation of the work function of fullerenes C{sub 60} and C{sub 70} by alkali-metal adsorption: A theoretical study

    Energy Technology Data Exchange (ETDEWEB)

    Liang, Hong [Institute of Architecture and Engineering, Weifang University of Science and Technology, Weifang 262700 (China); Xu, Shunfu, E-mail: xushunfu2009@gmail.com [Institute of Architecture and Engineering, Weifang University of Science and Technology, Weifang 262700 (China); Department of Physics, Institute of Information Science and Engineering, Ocean University of China, Qingdao 266100 (China); Liu, Weihui [Department of Physics, Institute of Information Science and Engineering, Ocean University of China, Qingdao 266100 (China); Sun, Yueqiang; Liu, Xiangfa; Zheng, Xinqing; Li, Sen; Zhang, Qiang; Zhu, Ziliang; Zhang, Xiaochun; Dong, Chengguo [Institute of Architecture and Engineering, Weifang University of Science and Technology, Weifang 262700 (China); Li, Chun [Department of Physics, Institute of Information Science and Engineering, Ocean University of China, Qingdao 266100 (China); Yuan, Guang, E-mail: yuanguang@ouc.edu.cn [Department of Physics, Institute of Information Science and Engineering, Ocean University of China, Qingdao 266100 (China); Research Institute of Electronics, University of Shizuoka, Hamamasu 432-8011 (Japan); Mimura, Hitenori [Department of Physics, Institute of Information Science and Engineering, Ocean University of China, Qingdao 266100 (China)

    2013-11-15

    The impact of alkali-metal (Li/Na/Cs) adsorption on work function of fullerenes C{sub 60} and C{sub 70} was investigated by first-principles calculations. After adsorption, the work functions of fullerenes C{sub 60} and C{sub 70} decrease distinctly and vary linearly with the electronegativity of the alkali metal elements, and the positions where the alkali atoms are adsorbed considerably influence the work functions. On the contrary, a vacancy defect elevates the work functions of the fullerenes C{sub 60} and C{sub 70}. The variation in the work functions rests with variation in Fermi level (which are attributed to charge transfer) and variation in vacuum levels (which are attributed to the induced dipole moments). Moreover, alkali-metal adsorption can also improve the electric conductivity of a fullerene mixture of C{sub 60} and C{sub 70}.

  4. Adsorption of superfluid 4He films on planar heavy-alkali metals studied with the Orsay-Trento density functional

    Science.gov (United States)

    Szybisz, Leszek

    2003-04-01

    The wetting of planar surfaces of alkali metals (Cs, Rb, K, and Na) by superfluid 4He films at T=0 K is theoretically studied. Calculations have been carried out by using the Orsay-Trento nonlocal density functional and the adsorption potential of Chizmeshya-Cole-Zaremba. Surface tensions and contact angles are determined for several approximations. We find that the conclusion on the wetting of an Rb substrate is sensible to the gradient-gradient term in the functional and the softness of the He-metal interaction.

  5. Measures for simultaneous minimization of alkali related operating problems, Phase 2; Aatgaerder foer samtidig minimering av alkalirelaterade driftproblem, Etapp 2. Ramprogram

    Energy Technology Data Exchange (ETDEWEB)

    Gyllenhammar, Marianne; Herstad Svaerd, Solvie; Davidsson, Kent; Aamand, Lars-Erik; Steenari, Britt-Marie; Folkeson, Nicklas; Pettersson, Jesper; Svensson, Jan-Erik; Boss, Anna; Johansson, Linda; Kassman, Haakan

    2007-12-15

    Combustion of an increasing amount of biofuel and waste woods has resulted in certain environmental advantages, including decreased emissions of fossil CO{sub 2}, SO{sub 2} and metals. On the other hand, a number of chloride and alkali related operational problems have occurred which are related to combustion of these fuels. Alkali related operational problems have been studied in a project consisting of two parts. The overall scope has been to characterise the operational problems and to study measures to minimise them. The first part was reported in Vaermeforsk report 997. In part two, additional measures have been included in the test plan and initial corrosion has been studied linked to the different measures. The tests have also in part two been carried out at the 12 MW CFB boiler at Chalmers. The effect of the selected measures has been investigated concerning both deposit formation and bed agglomeration, and at the same time emissions and other operational conditions were characterised. The second part of the project has among other things focused on: To investigate measures which decrease the content of alkali and chloride in the deposits, and consequently decrease the risk for corrosion (by investigating the initial corrosion). Focus was also on trying to explain favourable effects. To investigate if it is possible to combine a rather low dosage of kaolin and injection of ammonium sulphate. This was done in order to reduce both bed agglomeration and problems from deposits during combustion of fuels rich in chlorine. To investigate if co-combustion with sewage sludge, de-inking sludge or peat with high ash content, could give similar advantages as conventional additives. Investigate if ash from PFBC (coal ash and dolomite) is possible to use as an alternative bed material. In the reference case, straw pellets were co-combusted together with wood pellets. This fuel mixture gave high alkali and chlorine contents. Alkali was in surplus of chlorine. The

  6. Experimental and Theoretical Studies of Pressure Broadened Alkali-Metal Atom Resonance Lines

    Science.gov (United States)

    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.

  7. Study on the Characteristics of an Alkali-Metal Thermoelectric Power Generation System

    Science.gov (United States)

    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.

  8. Thermal Decomposition of Anhydrous Alkali Metal Dodecaborates M2B12H12 (M = Li, Na, K

    Directory of Open Access Journals (Sweden)

    Liqing He

    2015-11-01

    Full Text Available Metal dodecaborates M2/nB12H12 are regarded as the dehydrogenation intermediates of metal borohydrides M(BH4n that are expected to be high density hydrogen storage materials. In this work, thermal decomposition processes of anhydrous alkali metal dodecaborates M2B12H12 (M = Li, Na, K synthesized by sintering of MBH4 (M = Li, Na, K and B10H14 have been systematically investigated in order to understand its role in the dehydrogenation of M(BH4n. Thermal decomposition of M2B12H12 indicates multistep pathways accompanying the formation of H-deficient monomers M2B12H12−x containing the icosahedral B12 skeletons and is followed by the formation of (M2B12Hzn polymers. The decomposition behaviors are different with the in situ formed M2B12H12 during the dehydrogenation of metal borohydrides.

  9. Heat transfer and flow in high-temperature alkali-metal heat pipes

    Science.gov (United States)

    Nosach, N. A.; Gontarev, Iu. K.; Prisniakov, V. F.; Iakovenko, A. G.; Kostornov, A. G.

    1982-06-01

    An experimental study of the dynamics of heat pipes with steel wool and metal fiber wicks, in particular of startup and transition from one operating mode to another, is presented. The dynamics effect of the initial heat flux in the evaporator when NaK is the working fluid is determined. The effect of interaction between the liquid and vapor phases on the heat and mass transfer from the vapor condensing on the pipe wall is analyzed.

  10. Measures for simultaneous minimization of alkali related operating problems, Phase 2; Aatgaerder foer samtidig minimering av alkalirelaterade driftproblem, Etapp 2. Ramprogram

    Energy Technology Data Exchange (ETDEWEB)

    Gyllenhammar, Marianne; Herstad Svaerd, Solvie; Davidsson, Kent; Aamand, Lars-Erik; Steenari, Britt-Marie; Folkeson, Nicklas; Pettersson, Jesper; Svensson, Jan-Erik; Boss, Anna; Johansson, Linda; Kassman, Haakan

    2007-12-15

    Combustion of an increasing amount of biofuel and waste woods has resulted in certain environmental advantages, including decreased emissions of fossil CO{sub 2}, SO{sub 2} and metals. On the other hand, a number of chloride and alkali related operational problems have occurred which are related to combustion of these fuels. Alkali related operational problems have been studied in a project consisting of two parts. The overall scope has been to characterise the operational problems and to study measures to minimise them. The first part was reported in Vaermeforsk report 997. In part two, additional measures have been included in the test plan and initial corrosion has been studied linked to the different measures. The tests have also in part two been carried out at the 12 MW CFB boiler at Chalmers. The effect of the selected measures has been investigated concerning both deposit formation and bed agglomeration, and at the same time emissions and other operational conditions were characterised. The second part of the project has among other things focused on: To investigate measures which decrease the content of alkali and chloride in the deposits, and consequently decrease the risk for corrosion (by investigating the initial corrosion). Focus was also on trying to explain favourable effects. To investigate if it is possible to combine a rather low dosage of kaolin and injection of ammonium sulphate. This was done in order to reduce both bed agglomeration and problems from deposits during combustion of fuels rich in chlorine. To investigate if co-combustion with sewage sludge, de-inking sludge or peat with high ash content, could give similar advantages as conventional additives. Investigate if ash from PFBC (coal ash and dolomite) is possible to use as an alternative bed material. In the reference case, straw pellets were co-combusted together with wood pellets. This fuel mixture gave high alkali and chlorine contents. Alkali was in surplus of chlorine. The

  11. Plasma assisted measurements of alkali metal concentrations in pressurised combustion processes

    Energy Technology Data Exchange (ETDEWEB)

    Hernberg, R.; Haeyrinen, V. [Tampere Univ. of Technology (Finland)

    1997-10-01

    In this project the continuous alkali measurement method plasma excited alkali resonance line spectroscopy (PEARLS) was developed, tested and demonstrated in pressurised combustion facilities. The PEARLS method has been developed at Tampere University of Technology (TUT). During 1994-1996 the PEARLS method was developed from the laboratory level to an industrial prototype. The alkali measuring instrument has been tested and used for regular measurements in four different pressurised combustion installations ranging up to industrial pilot scale. The installations are: (1) a pressurised entrained flow reactor (PEFR) at VTT Energy in Jyvaeskylae, Finland (2) a pressurised fluidised bed combustion facility, called FRED, at DMT in Essen, Germany. (3) a 10 MW pressurised circulating fluidised bed combustion pilot plant at Foster Wheeler Energia Oy in Karhula, Finland (4) PFBC Research Facility at ABB Carbon in Finspaang, Sweden

  12. Alkali-Metal-Ion-Functionalized Graphene Oxide as a Superior Anode Material for Sodium-Ion Batteries.

    Science.gov (United States)

    Wan, Fang; Li, Yu-Han; Liu, Dai-Huo; Guo, Jin-Zhi; Sun, Hai-Zhu; Zhang, Jing-Ping; Wu, Xing-Long

    2016-06-06

    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.

  13. Methane coupling reaction in an oxy-steam stream through an OH radical pathway by using supported alkali metal catalysts

    KAUST Repository

    Liang, Yin

    2014-03-24

    A universal reaction mechanism involved in the oxidative coupling of methane (OCM) is demonstrated under oxy-steam conditions using alkali-metal-based catalysts. Rigorous kinetic measurements indicated a reaction mechanism that is consistent with OH radical formation from a H 2O-O2 reaction followed by C-H activation in CH 4 with an OH radical. Thus, the presence of water enhances both the CH4 conversion rate and the C2 selectivity. This OH radical pathway that is selective for the OCM was observed for the catalyst without Mn, which suggests clearly that Mn is not the essential component in a selective OCM catalyst. The experiments with different catalyst compositions revealed that the OH.-mediated pathway proceeded in the presence of catalysts with different alkali metals (Na, K) and different oxo anions (W, Mo). This difference in catalytic activity for OH radical generation accounts for the different OCM selectivities. As a result, a high C2 yield is achievable by using Na2WO4/SiO2, which catalyzes the OH.-mediated pathway selectively. Make it methane: A universal reaction mechanism involved in the oxidative coupling of methane is demonstrated under oxy-stream conditions by using alkali-metal-based catalysts. Rigorous kinetic measurements indicated a reaction mechanism that is consistent with OH radical formation from an H2O-O2 reaction, followed by C-H activation in CH4 with an OH radical. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Alkali metal salts of rutin - Synthesis, spectroscopic (FT-IR, FT-Raman, UV-VIS), antioxidant and antimicrobial studies.

    Science.gov (United States)

    Samsonowicz, M; Kamińska, I; Kalinowska, M; Lewandowski, W

    2015-12-05

    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.

  15. Nuclear Wavepacket Dynamics of Alkali Adsorbates on Metal Surfaces Studied by Time-Resolved Second Harmonic Generation

    Directory of Open Access Journals (Sweden)

    Kazuya Watanabe

    2012-01-01

    Full Text Available This paper reviews recent efforts to understand the dynamics of coherent surface vibrations of alkali atoms adsorbed on metal surfaces. Time-resolved second harmonic generation is used for the coherent excitation and detection of the nuclear wavepacket dynamics of the surface modes. The principles of the measurement and the experimental details are described. The main focus is on coverage and excitation photon energy dependences of the coherent phonon dynamics for Na-, K-, and Cs-covered Cu(111. The excitation mechanism of the coherent phonon has been revealed by the ultrafast time-domain technique and theoretical modelings.

  16. Syntheses and Structures of Alkali Metal Rare Earth Polyphosphates CsLn(PO3)4 (Ln = La, Ce)

    Institute of Scientific and Technical Information of China (English)

    ZHU Jing; CHENG Wen-Dan; ZHANG Hao; WU Dong-Sheng; ZHAO Dan

    2008-01-01

    Alkali metal-rare earth polyphosphates, CsLn(PO3)4 (Ln = La, Ce), were synthesized by the high temperature solution reaction and studied by single-crystal X-ray diffraction technique. They crystallize in the monoclinic space group P21 (Z = 2) and feature infinite PO4 spiral chains linked with neighboring CsO10 and LnO8 polyhedra. In addition, theoretically calculated energy band structure and density of states (DOS) by the density functional theory(DFT) predict that the solid-state compound CsLa(PO3)4 possesses insulative character.

  17. Sensitive determination of the spin polarization of optically pumped alkali-metal atoms using near-resonant light

    Science.gov (United States)

    Ding, Zhichao; Long, Xingwu; Yuan, Jie; Fan, Zhenfang; Luo, Hui

    2016-09-01

    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.

  18. Catalysis by alkali and alkaline-earth metal ions in nucleophilic attack of methoxide ion on crown ethers bearing an intra-annular acetoxy group

    NARCIS (Netherlands)

    Cacciapaglia, Roberta; Lucente, Silvia; Mandolini, Luigi; Doorn, van Arie R.; Reinhoudt, David N.; Verboom, Willem

    1989-01-01

    Rates of reaction of methoxide ion with crown ethers bearing an intra-annular acetoxy group are markedly enhanced by alkali and alkaline-earth metal bromides as a result of much stronger interactions of the metal ions with transition states than with reactants. Rates of reactions of methoxide ion w

  19. Plasma assisted measurements of alkali metal concentrations in pressurized combustion processes

    Energy Technology Data Exchange (ETDEWEB)

    Hernberg, R.; Haeyrinen, V. [Tampere Univ. of Technology (Finland). Dept. of Physics

    1996-12-01

    The plasma assisted method for continuous measurement of alkali concentrations in product gas flows of pressurized energy processes will be tested and applied at the 1.6 MW PFBC/G facility at Delft University of Technology in the Netherlands. During the reporting period the alkali measuring device has been tested under pressurized conditions at VTT Energy, DMT, Foster-Wheeler Energia and ABB Carbon. Measurements in Delft will be performed during 1996 after installation of the hot gas filter. The original plan for measurements in Delft has been postponed due to schedule delays in Delft. The results are expected to give information about the influence of different process conditions on the generation of alkali vapours, the comparison of different methods for alkali measurement and the specific performance of our system. This will be the first test of the plasma assisted measurement method in a gasification process. The project belongs to the Joule II extension program under contract JOU2-CT93-0431. (author)

  20. Alkali metal and ammonium chlorides in water and heavy water (binary systems)

    CERN Document Server

    Cohen-Adad, R

    1991-01-01

    This volume surveys the data available in the literature for solid-fluid solubility equilibria plus selected solid-liquid-vapour equilibria, for binary systems containing alkali and ammonium chlorides in water or heavy water. Solubilities covered are lithium chloride, sodium chloride, potassium chloride, rubidium chloride, caesium chloride and ammonium chloride in water and heavy water.

  1. 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

    Science.gov (United States)

    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.

  2. Alkali metal adsorption on Ge(0 0 1)-c(2 × 4) surface: 0.25 monolayer of Na, K, Rb and Cs

    Energy Technology Data Exchange (ETDEWEB)

    Stankiewicz, B., E-mail: bst@ifd.uni.wroc.pl [Institute of Experimental Physics, University of Wrocław, Pl. Maxa Borna 9, 50-204 Wrocław (Poland); Mikołajczyk, P. [Nokia Solutions and Networks, Gen. J. Bema Str. 2, 50-265 Wrocław (Poland)

    2014-05-01

    Highlights: • We examine alkali metals adsorption on the Ge(0 0 1)-c(2 × 4) surface. • We calculated atomic and electronic structures using local-orbital and plane-waves methods. • We simulated expected scanning tunneling microscopy images. - Abstract: Alkali metals on Ge(0 0 1) surface reveal different adsorption energy depending on the initial substrate reconstruction and the adsorption site. The theoretical analysis of adsorption of 0.25 monolayer of alkali metals (Na, K, Rb and Cs) on Ge(0 0 1)-c(2 × 4) surface is presented. Stable adsorption sites are found and adsorption energy, atomic and electronic structures are given. The simulated STM images are also presented for the discussed adsorbed surface structures.

  3. Distribution and uptake of {sup 137}Cs in relation to alkali metals in a perhumid montane forest ecosystem

    Energy Technology Data Exchange (ETDEWEB)

    Chao, J.H. [Nuclear Science and Technology Development Center, National Tsing Hua University, Hsinchu 30013, Taiwan (China)], E-mail: jhchao@mx.nthu.edu.tw; Chiu, C.Y. [Research Center for Biodiversity, Academia Sinica, Taipei 11529, Taiwan (China); Lee, H.P. [Nuclear Science and Technology Development Center, National Tsing Hua University, Hsinchu 30013, Taiwan (China)

    2008-10-15

    We determined the content of radiocesium ({sup 137}Cs) and alkali metals in soils, plants (2 ferns, a shrub and moss) and rainwater collected in an undisturbed forest ecosystem. The {sup 137}Cs activity and the isotopic ratio of {sup 137}Cs/Cs in the samples were used to interpret the distribution and uptake of {sup 137}Cs and the alkali metals in plants. As a whole, the {sup 137}Cs in plants was assimilated together with K but was not dependent on Cs. Different adaptations of fern species collected in ecological niches cause them to have different {sup 137}Cs/Cs ratios. Diplopterygium glaucum is distributed at the edges of the forest; it usually has shallow organic layers, and the root takes up more stable Cs from mineral layers, leading to lower {sup 137}Cs/Cs ratios than that in the understory Plagiogyria formosana and Rhododendron formosanum species. The steady supply of stable Cs through the uptake by D. glaucum from deep soils may gradually dilute the {sup 137}Cs concentration and thus explain the lower {sup 137}Cs/Cs ratio in the fern samples. The {sup 137}Cs is predicted to be proportional to the Cs content across plant species in the biological cycle once isotopic equilibrium is attained.

  4. Purification and characterization of an extracellular, thermo-alkali-stable, metal tolerant laccase from Bacillus tequilensis SN4.

    Science.gov (United States)

    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.

  5. Synthesis and exchange properties of sulfonated poly(phenylene sulfide) with alkali metal ions in organic solvents

    Energy Technology Data Exchange (ETDEWEB)

    Son, Won Keun [Chungnam National Univ., Taejon (Korea, Republic of); Kim, Sang Hern [Taejon National Univ., Taejon (Korea, Republic of); Park, Soo Gil [Chungbuk National Univ., Cheongju (Korea, Republic of)

    2001-01-01

    Sulfonated poly(phenylene sulfide) (SPPS) polymers were prepared by sulfonation of poly[methyl[4-(phenylthio)phenyl] sulfonium trifluoromethanesulfonate] (PPST) with fumic sulfonic acid (10% SO{sub 3}-H{sub 2}SO{sub 4}) and demethylation with aqueous NaOH solution. The equilibrium constants of ion exchange reactions between alkali metal cations (Li{sup +}, Na{sup +}, and K{sup +}) and SPPS ion exchanger in organic solvents such as in organic solvents such as tetrahydrofuran (THF) and dioxane were measured. The equilibrium constants of ion exchange reactions increased as the polarity of the solvent increased, and the reaction temperature decreased. The equilibrium constants of the ion exchange reaction (K{sub eq}) also increased in the order of Li{sup +}, Na{sup +}, and K{sup +}. To elucidate the spontaneity of the exchange reaction in organic solvents, the enthalpy, entropy, and Gibbs free energy were calculated. The enthalpy of reaction ranged from -0.88 to -1.33 kcal/mol, entropy ranged from 1.42 to 4.41 cal/Kmol, and Gibbs free energy ranged from -1.03 to -2.55 kcal/mol. Therefore, the exchange reactions were spontaneous because the Gibbs free energies were negative. The SPPS ion exchanger and alkali metal ion bounding each other produced good ion exchange capability in organic solvents.

  6. Influence of alkali metal cations on the thermal, mechanical and morphological properties of rectorite/chitosan bio-nanocomposite films.

    Science.gov (United States)

    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.

  7. Molecular dynamics evidence for alkali-metal rattling in the β-pyrochlores, AOs2O6 (A = K, Rb, Cs).

    Science.gov (United States)

    Shoko, E; Peterson, V K; Kearley, G J

    2013-11-27

    We have used ab initio molecular dynamics simulations validated against inelastic neutron scattering data to study alkali-metal dynamics in the β-pyrochlore osmates AOs2O6 (A=K, Rb, Cs) at 300 K to gain insight into the microscopic nature of rattling dynamics in these materials. Our results provide new evidence at the microscopic level for rattling dynamics: (1) the elemental magnitude spectra calculated from the MD show a striking dominance by the alkali metals at low energies indicating weak coupling to the cage, (2) the atomic root-mean-square displacements for the alkali metals are significantly larger than for the other atoms, e.g., 25% and 150% larger than O and Os, respectively, in KOs2O6, and (3) motions of the alkali metals are weakly correlated to the dynamics in their immediate environment, e.g. K in KOs2O6 is 6 times less sensitive to its local environment than Os, indicating weak bonding of the K. There is broadening of the elemental spectra of the alkali metals from Cs to K corresponding to a similar broadening of the local potential around these atoms as determined from potential of mean-force calculations. This feature of the spectra is partly explained by the well-known increase in the relative cage volume with decreasing atomic size of the alkali metal. We find that for the smallest rattler in this series (K) the larger relative cage volume allows this atom freedom to explore a large space inside the cage leading to vibration at a broader range of frequencies, hence a broader spectrum. Thus, since K is considered the best rattler in this series, these findings suggest that a significant feature of a good rattler is the ability to vibrate at several different but closely spaced frequencies.

  8. Prospects for sympathetic cooling of polar molecules: NH with alkali-metal and alkaline-earth atoms--a new hope.

    Science.gov (United States)

    Soldán, Pavel; Zuchowski, Piotr S; Hutson, Jeremy M

    2009-01-01

    We explore the potential energy surfaces for NH molecules interacting with alkali-metal and alkaline-earth atoms using highly correlated ab initio electronic structure calculations. The surfaces for interaction with alkali-metal atoms have deep wells dominated by covalent forces. The resulting strong anisotropies will produce strongly inelastic collisions. The surfaces for interaction with alkaline-earth atoms have shallower wells that are dominated by induction and dispersion forces. For Be and Mg the anisotropy is small compared to the rotational constant of NH, so that collisions will be relatively weakly inelastic. Be and Mg are thus promising coolants for sympathetic cooling of NH to the ultracold regime.

  9. Release and sorption of alkali metals in coal fired combined cycle power systems; Freisetzung und Einbindung von Alkalimetallverbindungen in kohlebefeuerten Kombikraftwerken

    Energy Technology Data Exchange (ETDEWEB)

    Mueller, Michael

    2009-07-01

    Coal fired combined cycle power systems will be a sufficient way to increase the efficiency of coal combustion. However, combined cycle power systems require a reliable hot gas cleanup. Especially alkali metals, such as sodium and potassium, can lead to hot corrosion of the gas turbine blading if they condensate as sulphates. The actual work deals with the release and sorption of alkali metals in coal fired combined cycle power systems. The influence of coal composition, temperature and pressure on the release of alkali species in coal combustion was investigated and the relevant release mechanisms identified. Alumosilicate sorbents have been found that reduce the alkali concentration in the hot flue gas of the Circulating Pressurized Fluidized Bed Combustion 2{sup nd} Generation (CPFBC 2{sup nd} Gen.) at 750 C to values sufficient for use in a gas turbine. Accordingly, alumosilicate sorbents working at 1400 C have been found for the Pressurized Pulverized Coal Combustion (PPCC). The sorption mechanisms have been identified. Thermodynamic calculations were performed to upscale the results of the laboratory experiments to conditions prevailing in power systems. According to these calculations, there is no risk of hot corrosion in both processes. Furthermore, thermodynamic calculations were performed to investigate the behaviour of alkali metals in an IGCC with integrated hot gas cleanup and H{sub 2} membrane for CO{sub 2} sequestration. (orig.)

  10. Comparisons between adsorption and diffusion of alkali, alkaline earth metal atoms on silicene and those on silicane: Insight from first-principles calculations

    Science.gov (United States)

    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.

  11. Solubility of alkali metal halides in the ionic liquid [C4C1im][OTf].

    Science.gov (United States)

    Kuzmina, O; Bordes, E; Schmauck, J; Hunt, P A; Hallett, J P; Welton, T

    2016-06-28

    The solubilities of the metal halides LiF, LiCl, LiBr, LiI, NaF, NaCl, NaBr, NaI, KF, KCl, KBr, KI, RbCl, CsCl, CsI, were measured at temperatures ranging from 298.15 to 378.15 K in the ionic liquid 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([C4C1im][OTf]). Li(+), Na(+) and K(+) salts with anions matching the ionic liquid have also been investigated to determine how well these cations dissolve in [C4C1im][OTf]. This study compares the influence of metal cation and halide anion on the solubility of salts within this ionic liquid. The highest solubility found was for iodide salts, and the lowest solubility for the three fluoride salts. There is no outstanding difference in the solubility of salts with matching anions in comparison to halide salts. The experimental data were correlated employing several phase equilibria models, including ideal mixtures, van't Hoff, the λh (Buchowski) equation, the modified Apelblat equation, and the non-random two-liquid model (NRTL). It was found that the van't Hoff model gave the best correlation results. On the basis of the experimental data the thermodynamic dissolution parameters (ΔH, ΔS, and ΔG) were determined for the studied systems together with computed gas phase metathesis parameters. Dissolution depends on the energy difference between enthalpies of fusion and dissolution of the solute salt. This demonstrates that overcoming the lattice energy of the solid matrix is the key to the solubility of inorganic salts in ionic liquids.

  12. A curious interplay in the films of N-heterocyclic carbene Pt(II) complexes upon deposition of alkali metals.

    Science.gov (United States)

    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

    2016-05-06

    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.

  13. Thermal and optical properties of Nd3+ doped lead zinc borate glasses—Influence of alkali metal ions

    Science.gov (United States)

    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.

  14. Thermal and optical properties of Nd{sup 3+} doped lead zinc borate glasses—Influence of alkali metal ions

    Energy Technology Data Exchange (ETDEWEB)

    Sasi Kumar, M.V.; Rajesh, D.; Balakrishna, A. [Department of Physics, Sri Venkateswara University, Tirupati 517502 (India); Ratnakaram, Y.C., E-mail: ratnakaramsvu@gmail.com [Department of Physics, Sri Venkateswara University, Tirupati 517502 (India)

    2013-04-15

    In the present investigation a new series of six different Nd{sup 3+} 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, Ω{sub λ} (λ=2, 4 and 6) and in turn used to estimate radiative properties of certain transitions. Spectroscopic parameters such as transition probabilities (A{sub T}), branching ratios (β), radiative lifetimes (τ{sub R}) 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 (σ{sub P}) are obtained for all the observed emission transitions.

  15. A curious interplay in the films of N-heterocyclic carbene PtII complexes upon deposition of alkali metals

    Science.gov (United States)

    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.

  16. Temperature-Dependent Electrical Conductivity Measurements on Hydrated and Alkali-metal Intercalated Zeolite LTA and FAU

    Science.gov (United States)

    Yumoto, Kenji; Suzuki, Yoshinori; Wada, Noboru

    2007-03-01

    Zeolite LTA and FAU films were made from zeolite powders using a hydrothermal method. Electrical conductivity measurement were performed on the zeolite films in temperature range between 180 K and 430 K, using an LCR meter with the sweeping frequency varied from 20 to 1 MHz and drawing the Cole-Cole plots. The resistivities of both hydrated LTA and FAU zeolites increased with increasing the sample temperature from RT to 430 K, which might be caused by loss of water molecules from the pores of zeolite crystals. Also, the resistivities increased with decreasing the sample temperature from RT to 180 K, probably caused by freezing of water molecules in the zeolite. When the dehydrated zeolite samples were intercalated with alkali metals (Rb and K), the resistivities of the samples did not vary much at RT. However, the resistivities of the intercalated zeolite films decreased drastically by four orders of magnitude when the sample temperature was varied from RT to 180 K. We speculate that the dynamics of alkali atoms in the zeolite pores (electron-phonon scattering) may be responsible for the drastic change in the electrical conductivity.

  17. Rapid yet accurate first principle based predictions of alkali halide crystal phases using alchemical perturbation

    CERN Document Server

    Solovyeva, Alisa

    2016-01-01

    We assess the predictive power of alchemical perturbations for estimating fundamental properties in ionic crystals. Using density functional theory we have calculated formation energies, lattice constants, and bulk moduli for all sixteen iso-valence-electronic combinations of pure pristine alkali halides involving elements $A \\in \\{$Na, K, Rb, Cs$\\}$ and $X \\in \\{$F, Cl, Br, I$\\}$. For rock salt, zincblende and cesium chloride symmetry, alchemical Hellmann-Feynman derivatives, evaluated along lattice scans of sixteen reference crystals, have been obtained for all respective 16$\\times$15 combinations of reference and predicted target crystals. Mean absolute errors (MAE) are on par with density functional theory level of accuracy for energies and bulk modulus. Predicted lattice constants are less accurate. NaCl is the best reference salt for alchemical estimates of relative energies (MAE $<$ 40 meV/atom) while alkali fluorides are the worst. By contrast, lattice constants are predicted best using NaF as a re...

  18. First-principles study of a double-cation alkali metal borohydride LiK(BH{sub 4}){sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Xiao Xiaobing; Yu Weiyang; Tang Biyu [Key Laboratory of Low Dimensional Materials and Application Technology of the Ministry of Education, Department of Physics, Xiangtan University, Hunan Province, 411105 (China)], E-mail: tangbiyu@gxu.edu.cn

    2008-11-05

    Metal borohydrides have been attracting great interest as potential candidates for use as advanced hydrogen storage materials because of their high gravimetric hydrogen densities. In the present study, first-principles calculations have been performed for the newly reported dual-cation alkali metal borohydride LiK(BH{sub 4}){sub 2}, using density functional theory (DFT) within the generalized gradient approximation and the projected augmented wave method. LiK(BH{sub 4}){sub 2} is found to have an orthorhombic structure in the space group Pnma (No 62) with nearly ideal tetrahedral shape. It is an insulating material having a DFT-calculated wide band gap of 6.08 eV. Analysis of the electronic structure shows an ionic interaction between metal cations and (BH{sub 4}){sup -} and the covalent B-H interaction within the (BH{sub 4}){sup -} tetrahedron. The enthalpy of the formation reaction from primary elements is calculated and found to be -449.8 kJ mol{sup -1}. The decomposition temperature (T{sub dec}) of LiK(BH{sub 4}){sub 2} lies between those of LiBH{sub 4} and KBH{sub 4}, which suggests that the hydrogen decomposition temperature of metal borohydrides can be precisely adjusted by the appropriate combination of cations.

  19. Viscometric and thermodynamic studies of interactions in ternary solutions containing sucrose and aqueous alkali metal halides at 293.15, 303.15 and 313.15 K

    Indian Academy of Sciences (India)

    Reena Gupta; Mukhtar Singh

    2005-05-01

    Viscosities and densities of sucrose in aqueous alkali metal halide solutions of different concentrations in the temperature range 293.15 to 313.15 K have been measured. Partial molar volumes at infinite dilution ($V_{2}^{0}$) of sucrose determined from apparent molar volume ($\\phi_v$) have been utilized to estimate partial molar volumes of transfer ($V^{0}_{2,tr}$) for sucrose from water to alkali metal halide solutions. The viscosity data of alkali metal halides in purely aqueous solutions and in the presence of sucrose at different temperatures (293.15, 303.15 and 313.5 K) have been analysed by the Jones-Dole equation. The nature and magnitude of solute-solvent and solute-solute interactions have been discussed in terms of the values of limiting apparent molar volume ($\\phi^{0}_{v}$), slope ($S_{v}$) and coefficients of the Jones-Dole equation. The structuremaking and structure-breaking capacities of alkali metal halides in pure aqueous solutions and in the presence of sucrose have been ascertained from temperature dependence of $\\phi^{0}_{v}$.

  20. Vanadium oxide based cpd. useful as a cathode active material - is used in lithium or alkali metal batteries to prolong life cycles

    DEFF Research Database (Denmark)

    1997-01-01

    , V and oxygen where at least some of the V is in the tetravalent state. USE-(I) is a cathode active material in electric current producing storage cells. ADVANTAGE-Use of (I) in Li or alkali metal batteries gives prolonged life cycles.Storage cells using (I) have improved capacity during charge...

  1. Cation and anion dependence of stable geometries and stabilization energies of alkali metal cation complexes with FSA(-), FTA(-), and TFSA(-) anions: relationship with physicochemical properties of molten salts.

    Science.gov (United States)

    Tsuzuki, Seiji; Kubota, Keigo; Matsumoto, Hajime

    2013-12-19

    Stable geometries and stabilization energies (Eform) of the alkali metal complexes with bis(fluorosulfonyl)amide, (fluorosulfonyl)(trifluoromethylslufonyl)amide and bis(trifluoromethylsulfonyl)amide (FSA(-), FTA(-) and TFSA(-)) were studied by ab initio molecular orbital calculations. The FSA(-) complexes prefer the bidentate structures in which two oxygen atoms of two SO2 groups have contact with the metal cation. The FTA(-) and TFSA(-) complexes with Li(+) and Na(+) prefer the bidentate structures, while the FTA(-) and TFSA(-) complexes with Cs(+) prefer tridentate structures in which the metal cation has contact with two oxygen atoms of an SO2 group and one oxygen atom of another SO2 group. The two structures are nearly isoenergetic in the FTA(-) and TFSA(-) complexes with K(+) and Rb(+). The magnitude of Eform depends on the alkali metal cation significantly. The Eform calculated for the most stable TFSA(-) complexes with Li(+), Na(+), K(+), Rb(+) and Cs(+) cations at the MP2/6-311G** level are -137.2, -110.5, -101.1, -89.6, and -84.1 kcal/mol, respectively. The viscosity and ionic conductivity of the alkali TFSA molten salts have strong correlation with the magnitude of the attraction. The viscosity increases and the ionic conductivity decreases with the increase of the attraction. The melting points of the alkali TFSA and alkali BETA molten salts also have correlation with the magnitude of the Eform, which strongly suggests that the magnitude of the attraction play important roles in determining the melting points of these molten salts. The anion dependence of the Eform calculated for the complexes is small (less than 2.9 kcal/mol). This shows that the magnitude of the attraction is not the cause of the low melting points of alkali FTA molten salts compared with those of corresponding alkali TFSA molten salts. The electrostatic interactions are the major source of the attraction in the complexes. The electrostatic energies for the most stable TFSA

  2. Hyperfine-induced quadrupole moments of alkali-metal atom ground states and their implications for atomic clocks

    CERN Document Server

    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 non-vanishing 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 $^{133}$Cs atomic clocks, the spatial gradients of electric fields must be smaller than $30 \\, \\mathrm{V}/\\mathrm{cm}^2$ to guarantee fractional inaccuracies below $10^{-16}$.

  3. Measuring the spin polarization of alkali-metal atoms using nuclear magnetic resonance frequency shifts of noble gases

    Directory of Open Access Journals (Sweden)

    X. H. Liu

    2015-10-01

    Full Text Available 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.

  4. Measuring the spin polarization of alkali-metal atoms using nuclear magnetic resonance frequency shifts of noble gases

    Energy Technology Data Exchange (ETDEWEB)

    Liu, X. H.; Luo, H.; Qu, T. L., E-mail: qutianliang@nudt.edu.cn; Yang, K. Y.; Ding, Z. C. [College of Optoelectronic Science and Engineering, National University of Defense Technology, Changsha 410073 (China)

    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.

  5. The Trapping and Cooling of Alkalis Metal Atoms%碱金属原子的囚禁与冷却

    Institute of Scientific and Technical Information of China (English)

    邓海明; 李璋

    2012-01-01

      描述了如何利用激光以及磁场构建光学粘胶、激光阱、磁阱、磁光阱等实现对碱金属的囚禁与冷却,旨在明晰的呈现BEC实验实现的关键技术、物理原理以及各种装置的优缺点。%  This essay describes how to use laser and magnetic field to construct optical molasses ,laser trap ,mag-netic trap and magneto -optical trap to trap and cool alkali-metal atoms .It presents clearly the key experimental technologies of Bose-Einstein condensate ,the physical principle and the relative advantages and disadvantages of different equipments .

  6. One- and two-photon spectroscopy of highly excited states of alkali-metal atoms on helium nanodroplets.

    Science.gov (United States)

    Pifrader, Alexandra; Allard, Olivier; Auböck, 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 (≈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←ns transition of K, Rb, and Cs (n=4, 5, and 6, respectively) and on the two-photon one-color excitation of the 5d←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.

  7. Crown-Ether Derived Graphene Hybrid Composite for Membrane-Free Potentiometric Sensing of Alkali Metal Ions.

    Science.gov (United States)

    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.

  8. Synthesis and Crystal Structure of A New Armed-tetraazacrown Ether and Its Liquid Membrane Transport of Alkali Metal Cations

    Institute of Scientific and Technical Information of China (English)

    马淑兰; 朱文祥; 董淑静; 郭倩玲; 佘远斌

    2003-01-01

    A new tetra-N-substituted tetraazacrown ether derivative, 4,7,13,16-tetra ( 2-cyanobenzyl)-1, 10-dioxa-4, 7, 13, 16-tetraazacy-dooctademne, C44H48N8O2, has been synthesized and struc-turally characterized. It crystallizes in the monoclinic system,Slmeegroup P21/c with a = 1.1176(3) nm, b =2.1906(7) nm,c=0.8430(3)nm, V=2.0132(10)nm3, β = 102.740(5)°,Z=4, Dc= 1.189 g/cm3, final R1=0.0460, wR2=0.0803.The liquid membrane transports of alkali metal cations using the new macrocyde as the ion-carrier were also studied. Com-pared with some macrocyclic ligands, our newly synthesized lig.and showed a good selectivity ratio for Na Na+/Li+.

  9. Alkali Metal Halide Salts as Interface Additives to Fabricate Hysteresis-Free Hybrid Perovskite-Based Photovoltaic Devices.

    Science.gov (United States)

    Wang, Lili; Moghe, Dhanashree; Hafezian, Soroush; Chen, Pei; Young, Margaret; Elinski, Mark; Martinu, Ludvik; Kéna-Cohen, Stéphane; Lunt, Richard R

    2016-09-07

    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.

  10. Purification and characterization of an extracellular, thermo-alkali-stable, metal tolerant laccase from Bacillus tequilensis SN4.

    Directory of Open Access Journals (Sweden)

    Sonica Sondhi

    Full Text Available 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.

  11. Partial Oxidation of Butane to Syngas over Nickel SupportedCatalysts Modified by Alkali Metal Oxide and Rare-Earth Metal Oxide

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The partial oxidation of butane (POB) to syngas over nickel supported catalysts was first investigated with a flow-reactor, TG and UVRRS. The NiO/g-Al2O3 is the most suitable for the POB among NiO/g-Al2O3, NiO/MgO and NiO/SiO2. And the reaction performance of the NiO/g-Al2O3 shows little difference from those of the nickel supported catalysts modified by alkali metal oxide and rare-earth metal oxide. However, modification with Li2O and La2O3 can suppress carbon-deposition of the NiO/g-Al2O3, which contains graphite-like species during the POB reaction.

  12. Ion chromatography with the indirect ultraviolet detection of alkali metal ions and ammonium using imidazolium ionic liquid as ultraviolet absorption reagent and eluent.

    Science.gov (United States)

    Liu, Yong-Qiang; Yu, Hong

    2016-08-01

    Indirect ultraviolet detection was conducted in ultraviolet-absorption-agent-added mobile phase to complete the detection of the absence of ultraviolet absorption functional group in analytes. Compared with precolumn derivatization or postcolumn derivatization, this method can be widely used, has the advantages of simple operation and good linear relationship. Chromatographic separation of Li(+) , Na(+) , K(+) , and NH4 (+) was performed on a carboxylic acid base cation exchange column using imidazolium ionic liquid/acid/organic solvent as the mobile phase, in which imidazolium ionic liquids acted as ultraviolet absorption reagent and eluting agent. The retention behaviors of four kinds of cations are discussed, and the mechanism of separation and detection are described. The main factors influencing the separation and detection were the background ultraviolet absorption reagent and the concentration of hydrogen ion in the ion chromatography-indirect ultraviolet detection. The successful separation and detection of Li(+) , Na(+) , K(+) , and NH4 (+) within 13 min was achieved using the selected chromatographic conditions, and the detection limits (S/N = 3) were 0.02, 0.11, 0.30, and 0.06 mg/L, respectively. A new separation and analysis method of alkali metal ions and ammonium by ion chromatography with indirect ultraviolet detection method was developed, and the application range of ionic liquid was expanded.

  13. Cation-π interaction of alkali metal ions with C24 fullerene: a DFT study.

    Science.gov (United States)

    Moradi, Morteza; Peyghan, Ali Ahmadi; Bagheri, Zargham; Kamfiroozi, Mohammad

    2012-08-01

    Using first principle calculations, we investigated cation-π interactions between alkali cations (Li(+), Na(+), and K(+)) and pristine C(24) or doped fullerenes of BC(23), and NC(23). The most suitable adsorption site is found to be atop the center of a six-membered ring of the exterior surface of C(24) molecule. Interaction energies of these cations decreased in the order: Li(+) > Na(+) > K(+), with values of -31.82, -22.36, and -15.68 kcal mol(-1), respectively. It was shown that the interaction energies are increased and decreased by impurity doping of B and N atoms in adjacent wall of adsorption site, depending on electron donating or receptivity of the doping atoms.

  14. First structural evidence for multiple alkali metals between sandwich decks in a metallocene.

    Science.gov (United States)

    Jeletic, Matthew; Perras, Frédéric A; Gorelsky, Serge I; Le Roy, Jennifer J; Korobkov, Ilia; Bryce, David L; Murugesu, Muralee

    2012-07-14

    A tetralithio salt (1) derived by treating 1,4-bis(trimethylsilyl)-cyclooctatriene with (n)BuLi serves as the first structural evidence for a multi-alkali metallocene. Single-crystal XRD confirms two Li(+) each asymmetrically bind to η(3) and η(4) between two COT'' rings and two Li(+) terminally bind to η(3). Solid-state NMR studies confirm the presence of two distinct lithium ion sites while the solution NMR studies suggest the formation of an (COT'' dianion) ion-pair in solution. Further treating of the tetralithio salt with NaCl leads to linear sodium polymeric chains. Therefore, simply changing the ionic radius changes the molecular structure.

  15. Phase transformations in metallic glasses

    DEFF Research Database (Denmark)

    Jiang, Jianzhong

    2003-01-01

    Recent development of grain-size effect on phase transformations induced by pressure is reported. A thermodynamic theory is presented and three components: the ratio of volume collapses, the surface energy differences, and the internal energy differences, governing the change of transition pressu...

  16. Theory of alkali-metal-induced reconstructions of fcc(100) surfaces

    DEFF Research Database (Denmark)

    Christensen, Ole Bøssing; Jacobsen, Karsten Wedel

    1992-01-01

    Calculations of missing-row reconstruction energies of the fcc(100) surfaces of the metals Al, Ni, Pd, Pt, Cu, Ag, and Au have been performed with the effective-medium theory with and without the presence of a potassium overlayer. It is shown that the tendency to reconstruct in the presence......-metal-induced reconstruction of fcc(110) surfaces are pointed out....

  17. The electronic properties of bare and alkali metal adsorbed two-dimensional GeSi alloy sheet

    Science.gov (United States)

    Qiu, Wenhao; Ye, Han; Yu, Zhongyuan; Liu, Yumin

    2016-09-01

    In this paper, the structural and electronic properties of both bare and alkali metal (AM) atoms adsorbed two-dimensional GeSi alloy sheet (GeSiAS) are investigated by means of first-principles calculations. The band gaps of bare GeSiAS are shown slightly opened at Dirac point with the energy dispersion remain linear due to the spin-orbit coupling effect at all concentrations of Ge atoms. For metal adsorption, AM atoms (including Li, Na and K) prefer to occupy the hexagonal hollow site of GeSiAS and the primary chemical bond between AM adatom and GeSiAS is ionic. The adsorption energy has an increase tendency with the increase of the Ge concentration in supercell. Besides, single-side adsorption of AM atoms introduces band gap at Dirac point, which can be tuned by the Ge concentration and the species of AM atoms. The strong relation between the band gaps and the distribution of Si and Ge atoms inside GeSiAS are also demonstrated. The opened band gaps of AM covered GeSiAS range from 14.8 to 269.1 meV along with the effective masses of electrons ranging from 0.013 to 0.109 me, indicating the high tunability of band gap as well as high mobility of carriers. These results provide a development in two-dimensional alloys and show potential applications in novel micro/nano-electronic devices.

  18. Atomic many-body effects and Lamb shifts in alkali metals

    CERN Document Server

    Ginges, J S M

    2016-01-01

    We present a detailed study of the Flambaum-Ginges radiative potential method which enables the accurate inclusion of quantum electrodynamics (QED) radiative corrections in a simple manner in atoms, ions, and molecules 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 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 th...

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

    Science.gov (United States)

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

    2016-04-05

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

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

    Science.gov (United States)

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

    2016-04-01

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

  1. ALKALI RESISTANT CATALYST

    DEFF Research Database (Denmark)

    2008-01-01

    The present invention concerns the selective removal of nitrogen oxides (NOx) from gasses. In particular, the invention concerns a process, a catalyst and the use of a catalyst for the selective removal of nitrogen oxides in the presence of ammonia from gases containing a significant amount...... of alkali metal and/or alkali-earth compounds which process comprises using a catalyst combined of (i) a formed porous superacidic support, said superacidic support having an Hammett acidity stronger than Ho=-12, and (ii) a metal oxide catalytic component deposited on said superacidic support selected from...

  2. Alkali Metal Rankine Cycle Boiler Technology Challenges and Some Potential Solutions for Space Nuclear Power and Propulsion Applications

    Science.gov (United States)

    Stone, James R.

    1994-01-01

    Alkali metal boilers are of interest for application to future space Rankine cycle power conversion systems. Significant progress on such boilers was accomplished in the 1960's and early 1970's, but development was not continued to operational systems since NASA's plans for future space missions were drastically curtailed in the early 1970's. In particular, piloted Mars missions were indefinitely deferred. With the announcement of the Space Exploration Initiative (SEI) in July 1989 by President Bush, interest was rekindled in challenging space missions and, consequently in space nuclear power and propulsion. Nuclear electric propulsion (NEP) and nuclear thermal propulsion (NTP) were proposed for interplanetary space vehicles, particularly for Mars missions. The potassium Rankine power conversion cycle became of interest to provide electric power for NEP vehicles and for 'dual-mode' NTP vehicles, where the same reactor could be used directly for propulsion and (with an additional coolant loop) for power. Although the boiler is not a major contributor to system mass, it is of critical importance because of its interaction with the rest of the power conversion system; it can cause problems for other components such as excess liquid droplets entering the turbine, thereby reducing its life, or more critically, it can drive instabilities-some severe enough to cause system failure. Funding for the SEI and its associated technology program from 1990 to 1993 was not sufficient to support significant new work on Rankine cycle boilers for space applications. In Fiscal Year 1994, funding for these challenging missions and technologies has again been curtailed, and planning for the future is very uncertain. The purpose of this paper is to review the technologies developed in the 1960's and 1970's in the light of the recent SEI applications. In this way, future Rankine cycle boiler programs may be conducted most efficiently. This report is aimed at evaluating alkali metal boiler

  3. Adsorption of alkali, alkaline-earth, simple and 3d transition metal, and nonmetal atoms on monolayer MoS2

    Directory of Open Access Journals (Sweden)

    X. D. Li

    2015-05-01

    Full Text Available Single adsorption of different atoms on pristine two-dimensional monolayer MoS2 have been systematically investigated by using density functional calculations with van der Waals correction. The adatoms cover alkali metals, alkaline earth metals, main group metal, 3d-transition metals, coinage metal and nonmetal atoms. Depending on the adatom type, metallic, semimetallic or semiconducting behavior can be found in direct bandgap monolayer MoS2. Additionally, local or long-range magnetic moments of two-dimensional MoS2 sheet can also attained through the adsorption. The detailed atomic-scale knowledge of single adsorption on MoS2 monolayer is important not only for the sake of a theoretical understanding, but also device level deposition technological application.

  4. Structural and optical characterization of Er-alkali-metals codoped MgO nanoparticles synthesized by solution combustion route

    Science.gov (United States)

    Sivasankari, J.; Selvakumar Sellaiyan, S.; Sankar, S.; Devi, L. Vimala; Sivaji, K.

    2017-01-01

    Pure MgO, rare-earth (Er) doped MgO (MgO:Er), and alkali metal ions (Li, Na and K) co-doped MgO:Er [i.e. MgO: Er+X (X=Li, Na, and K)] nanopowders were synthesized by solution combustion method and characterized. The XRD analysis reveals the cubic structure and the substitution of dopants and co-dopants in MgO. Annealing at 800 °C, increases the sizes of nano-crystallites of all samples appreciably, indicating the grain growth and the improvement in crystallinity of all the samples. Increase in lattice parameter, d spacing and band gap were observed after annealing. Structural and morphological analysis using scanning electron microscope (SEM) and transmission electron microscope (TEM) studies has shown that the samples contain structures like agglomerated clusters. FT-IR spectra confirm the stretching mode of hydroxyl groups, carbonate and presence of MgO bonding. The characteristic wavelength ranging from 2600 cm-1 to 3000 cm-1 were assigned to transition of 4S3/2→4I13/2 and 4I11/2→4I15/2 of Er3+.

  5. Effect of semicore banding on heavy-alkali-metal lattice constants: Corrections to the frozen-core approximation

    Science.gov (United States)

    Yang, L. H.; Smith, A. P.; Benedek, R.; Koelling, D. D.

    1993-06-01

    Equilibrium lattice constants and bulk moduli of the heavy alkali metals K, Rb, and Cs were calculated using the Troullier-Martins pseudopotentials and plane-wave basis functions. The treatment of the outermost p-shell electrons as Bloch states yielded lattice constants 2-3 % larger than those obtained within the frozen-core approximation (including the partial core correction of Louie, Froyen, and Cohen [Phys. Rev. B 26, 1738 (1982)]), which narrows a long-standing discrepancy between local-density functional theory and experiment. Predicted bulk moduli are 30-50 % larger than measured values, within either treatment. The band dispersion of the semicore states (with bandwidths 0.067, 0.14, and 0.25 eV for K, Rb, and Cs) is attributed primarily to core-electron-conduction-electron hybridization rather than direct core-core overlap. The semicore density of states has a flat line shape, rather than the peaked shape expected for an idealized tight-binding band.

  6. Fates and roles of alkali and alkaline earth metal species during the pyrolysis and gasification of a Victorian lignite

    Energy Technology Data Exchange (ETDEWEB)

    Mody, D.; Wu, H.; Li, C. [Monash University, Vic. (Australia). CRC for Clean Power from Lignite, Dept. of Chemical Engineering

    2000-07-01

    The transformation of alkali and alkaline earth metal (AAEM) species in a Victorian lignite during the pyrolysis and subsequent gasification in CO{sub 2} was studied in a novel quartz fluidised-bed reactor. Lignite samples prepared by physically adding NaCl and ion-exchanging Na{sup +} and Ca{sup ++} into the lignite were used to investigate the effects of chemical forms and valency of the AAEM species in the substrate lignite on their transformation during pyrolysis and gasification. Carboxyl-bound Na was found to be less volatile than Na present as NaCl, but more volatile than carboxyl-bound Ca during pyrolysis at temperatures between 400 and 900{sup o}C. However, the carboxyl-bound Na was volatilised to a much greater extent than the carboxyl-bound Ca in the same lignite during pyrolysis. It was seen that the loading of NaCl into the lignite did not significantly affect the char reactivity in the fluidised-bed reactor at 900{sup o}C.

  7. Effect of charge density in chain extension reactions involving complexes of 4, 4'-diaminodiphenylmethane and various alkali metal salts

    Science.gov (United States)

    Deshmukh, Subrajeet; Carrasquillo, Katherine; Tsai, Fang Chang; Wu, Lina; Hsu, Shaw Ling; University of Massachusetts Amherst Team

    Controlling the reaction of methylene diphenyl diisocyanate (MDI)-terminated polyester prepolymer and 4, 4'-diaminodiphenylmethane (MDA) is extremely important in many large scale applications. The ion-diamine complex has the advantage of blocking the instantaneous reaction between the diamine and isocyanate from taking place until it is released at elevated temperatures. We synthesized complexes of MDA with various alkali metal salts. These complexes create a barrier between the diamine and isocyanate thus preventing the premature reaction. We compared the complexes in terms of their dissociation and the subsequent curing with the prepolymer. Charge density had a tremendous effect. DSC showed that Na complexes dissociated at a lower temperature and needed less energy to dissociate than the Li complexes. The effect of change in cation on complex dissociation was more pronounced compared to the change in anion. Also, the ionic liquid introduced greatly altered the dissociation behavior. Temperature and time resolved IR spectroscopy was used to monitor the urea and NH band. By DSC and IR, we showed that NaCl complex is best suited for the curing of prepolymer with regards to curing temperature and energy.

  8. Chemical state analysis of trace-level alkali metals sorbed in micaceous oxide by total reflection X-ray photoelectron spectroscopy

    Science.gov (United States)

    Baba, Y.; Shimoyama, I.; Hirao, N.

    2016-10-01

    In order to determine the chemical states of radioactive cesium (137Cs or 134Cs) sorbed in clay minerals, chemical states of cesium as well as the other alkali metals (sodium and rubidium) sorbed in micaceous oxides have been investigated by X-ray photoelectron spectroscopy (XPS). Since the number of atoms in radioactive cesium is extremely small, we specially focused on chemical states of trace-level alkali metals. For this purpose, we have measured XPS under X-ray total reflection (TR) condition. For cesium, it was shown that ultra-trace amount of cesium down to about 100 pg cm-2 can be detected by TR-XPS. This amount corresponds to about 200 Bq of 137Cs (t1/2 = 30.2 y). It was demonstrated that ultra-trace amount of cesium corresponding to radioactive cesium level can be measured by TR-XPS. As to the chemical states, it was found that core-level binding energy in TR-XPS for trace-level cesium shifted to lower-energy side compared with that for thicker layer. A reverse tendency is observed in sodium. Based on charge transfer within a simple point-charge model, it is concluded that chemical bond between alkali metal and micaceous oxide for ultra-thin layer is more polarized that for thick layer.

  9. 异核碱金属原子间的三体相互作用系数%Three-body dispersion coefficients for heteronuclear alkali-metal atoms

    Institute of Scientific and Technical Information of China (English)

    谢柏东; 黄时中

    2013-01-01

    By utilizing the model potential for alkali-metal atoms and the variationally stable method, the three-body dispersion coefficients for heteronuclear interactions of the alkali-metal atoms are calculated for the first time. In order to illustrate the reliability of the calculated results, the multipolar polarizabil-ities of the alkali-metal atoms are also calculated and compared with those of the previous calculations and experimental data. The results show that the present three-body dispersion coefficients are reliable.%利用碱金属原子的模型势和稳定变分法,首次计算了异核碱金属原子间的三体相互作用系数.为了说明计算结果的精度,同时计算了碱金属原子的电多级极化率.与其他作者的理论数据和有关实验数据的比较表明,本文所得到的异核碱金属原子间的三体相互作用系数是可靠的.

  10. Partial alkali-metal ion extraction from K0.8(Li0.27Ti1.73)O4 using PTFE as an extraction reagent.

    Science.gov (United States)

    Ozawa, Tadashi C; Sasaki, Takayoshi

    2014-10-21

    The alkali-metal ion extraction ability of an inert material, polytetrafluoroethylene (PTFE; empirical formula CF2), was clarified by characterizing a partially alkali-metal ion-extracted layered compound, K0.8(Li0.27Ti1.73)O4. Washing K0.8(Li0.27Ti1.73)O4 in water extracts only 44% of the interlayer K(+) and no intralayer Li(+); on the other hand, 53% of the interlayer K(+) and approximately 10% of the intralayer Li(+) ions were extracted from K0.8(Li0.27Ti1.73)O4 by the reaction with PTFE at 350 °C under flowing Ar. A systematic decrease in the lattice parameters a and c along the intralayer directions and an increase in b along the interlayer direction were observed, consistent with the alkali-metal ion deintercalation amount as a function of the reaction temperatures and the reacted PTFE amounts. After the reaction with K0.8(Li0.27Ti1.73)O4 : CF2 = 1 : 0.6 in mol, the lattice parameter b increased to 1.5607(3) nm from 1.5522(2) of the pristine K0.8(Li0.27Ti1.73)O4, and this change in the lattice parameter was approximately one order of magnitude larger than those in a and c.

  11. Influence of alkali metal superoxides on structure, electronic, and optical properties of Be12O12 nanocage: Density functional theory study

    Science.gov (United States)

    Raoof Toosi, Ali; Shamlouei, Hamid Reza; Hesari, Asghar Mohammadi

    2016-09-01

    The effect of alkali metal superoxides M3O (M = Li, Na, K) on the electronic and optical properties of a Be12O12 nanocage was studied by density functional theory (DFT) and time-dependent density functional theory (TD-DFT). The energy gaps (Eg) of all configurations were calculated. Generally, the adsorption of alkali metal superoxides on the Be12O12 nanocage causes a decrease of Eg. Electric dipole moment μ, polarizability α, and static first hyperpolarizability β were calculated and it was shown that the adsorption of alkali metal superoxides on Be12O12 increases its polarizability. It was found that the absorption of M3O on Be12O12 nanocluster improves its nonlinear optical properties. The highest first hyperpolarizability (β ≈ 214000 a.u.) is obtained in the K3O-Be12O12 nanocluster. The TD-DFT calculations were performed to investigate the origin of the first hyperpolarizabilities and it was shown that a higher first hyperpolarizability belongs to the structure that has a lower transition energy.

  12. A negative ion source for alkali ions

    NARCIS (Netherlands)

    Vermeer, A.; Zwol, N.A. van

    1980-01-01

    An ion source is described which delivers negative alkali ions. With this source, which consists of a duoplasmatron and a charge exchange canal with alkali vapour, negative Li, Na and K ions are produced. The oven in which alkali metals are evaporated can reach temperatures up to 575°C.

  13. Effects of Alkali and Alkaline Earth Metals on N-Containing Species Release during Rice Straw Pyrolysis

    Directory of Open Access Journals (Sweden)

    Pan Gao

    2015-11-01

    Full Text Available To study the effects of inherent and external alkali and alkaline earth metallic species (AAEMs, i.e., K, Ca and Mg on the behavior of N-containing species release during rice straw (RS pyrolysis, different pretreatments were applied in numerous experiments. Results indicate that ammonia (NH3 and hydrogen cyanide (HCN are the major N-containing species and that the yields of isocyanic acid (HNCO and nitric oxide (NO are relatively low. The removal of inhert AAEMs shifts N-containing species release to a high-temperature zone according to volatile release behavior because of the increase in activation energy. The formation selectivity of NH3, HNCO, and NO increases by demineralized pretreatment, whereas HCN selectivity decreases. The formation of HNCO is mainly affected by alkaline earth metal. N-containing species release occurs in low temperatures with the addition of external AAEMs. The activation energy of samples impregnated with CaCl2 and MgCl2 sharply decreases compared to the original RS. The total yields of N-containing species are reduced significantly in the presence of KCl, CaCl2, and MgCl2 as additives. The inhibition ability of AAEMs follows the sequence MgCl2 > CaCl2 > KCl. The inhibition effect of MgCl2 can be improved by solution immersion compared with solid powder mixing. The clean biomass pyrolysis and gasification technology with low N-containing species content may be developed according to the results.

  14. Dipole Polarizability of Alkali-Metal (Na, K, Rb) - Alkaline-Earth-Metal (Ca,Sr) Polar molecules - Prospects of Alignment

    CERN Document Server

    Gopakumar, Geetha; Hada, Masahiko; Kajita, Masatoshi

    2014-01-01

    Electronic open-shell ground-state properties of selected alkali-metal (AM) - alkaline-earth-metal (AEM) polar molecules are investigated. We determine potential energy curves of the 2{\\Sigma}+ ground state at the coupled-cluster singles and doubles with partial triples (CCSD(T)) level of electron correlation. Calculated spectroscopic constants for the isotopes (23Na, 39K, 85Rb) - (40Ca, 88Sr) are compared with available theoretical and experimental results. The variation of the permanent dipole moment (PDM), average dipole polarizability, and polarizability anisotropy with internuclear distance is determined using finite-field perturbation theory at the CCSD(T) level. Owing to moderate PDM (KCa: 1.67 D, RbCa: 1.75 D, KSr: 1.27 D, RbSr: 1.41 D) and large polarizability anisotropy (KCa: 566 a.u., RbCa: 604 a.u., KSr: 574 a.u., RbSr: 615 a.u.), KCa, RbCa, KSr, and RbSr are potential candidates for alignment and orientation in combined intense laser and external static electric fields.

  15. Alkali metal – yttrium borohydrides: The link between coordination of small and large rare-earth

    Energy Technology Data Exchange (ETDEWEB)

    Sadikin, Yolanda [Department of Quantum Matter Physics, Laboratory of Crystallography, University of Geneva, Quai Ernest-Ansermet 24, CH-1211 Geneva (Switzerland); Stare, Katarina [Department of Quantum Matter Physics, Laboratory of Crystallography, University of Geneva, Quai Ernest-Ansermet 24, CH-1211 Geneva (Switzerland); Faculty of Chemistry and Chemical Technology, University of Ljubljana, Aškerjeva 5, SI-1000 Ljubljana (Slovenia); Schouwink, Pascal [Department of Quantum Matter Physics, Laboratory of Crystallography, University of Geneva, Quai Ernest-Ansermet 24, CH-1211 Geneva (Switzerland); Brix Ley, Morten; Jensen, Torben R. [Center for Materials Crystallography (CMC), Interdisciplinary Nanoscience Center (iNANO), and Department of Chemistry, Aarhus University, Langelandsgade 140, DK-8000 Århus C (Denmark); Meden, Anton [Faculty of Chemistry and Chemical Technology, University of Ljubljana, Aškerjeva 5, SI-1000 Ljubljana (Slovenia); Černý, Radovan, E-mail: radovan.cerny@unige.ch [Department of Quantum Matter Physics, Laboratory of Crystallography, University of Geneva, Quai Ernest-Ansermet 24, CH-1211 Geneva (Switzerland)

    2015-05-15

    The system Li–A–Y–BH{sub 4} (A=K, Rb, Cs) is found to contain five new compounds and four further ones known from previous work on the homoleptic borohydrides. Crystal structures have been solved and refined from synchrotron X-ray powder diffraction, thermal stability of new compounds have been investigated and ionic conductivity measured for selected samples. Significant coordination flexibility for Y{sup 3+} is revealed, which allows the formation of both octahedral frameworks and tetrahedral complex anions with the tetrahydroborate anion BH{sub 4} both as a linker and terminal ligand. Bi- and trimetallic cubic double-perovskites c-A{sub 3}Y(BH{sub 4}){sub 6} or c-A{sub 2}LiY(BH{sub 4}){sub 6} (A=Rb, Cs) form in all the investigated systems, with the exception of the Li–K–Y system. The compounds with the stoichiometry AY(BH{sub 4}){sub 4} crystallize in all investigated systems with a great variety of structure types which find their analog amongst metal oxides. In-situ formation of a new borohydride – closo-borane is observed during decomposition of all double perovskites. - Graphical abstract: The system Li–A–Y–BH{sub 4} (A=K, Rb, Cs) is found to contain five novel compounds and four further ones previously reported. Significant coordination flexibility of Y{sup 3+} is revealed, which can be employed to form both octahedral frameworks and tetrahedral complex anions, very different structural topologies. Versatility is also manifested in three different simultaneously occurring coordination modes of borohydrides for one metal cation, as proposed by DFT optimization of the monoclinic KY(BH{sub 4}){sub 4} structural model observed by powder diffraction. - Highlights: • The system Li-A-Y-BH{sub 4} (A=K, Rb, Cs) contains nine compounds in total. • Y{sup 3+} forms octahedral frameworks and tetrahedral complex anions. • Bi- and trimetallic double-perovskites crystallize in most systems. • Various AY(BH{sub 4}){sub 4} crystallize with

  16. Complex formation during dissolution of metal oxides in molten alkali carbonates

    DEFF Research Database (Denmark)

    Li, Qingfeng; Borup, Flemming; Petrushina, Irina;

    1999-01-01

    Dissolution of metal oxides in molten carbonates relates directly to the stability of materials for electrodes and construction of molten carbonate fuel cells. In the present work the solubilities of PbO, NiO, Fe2O3,and Bi2O3 in molten Li/K carbonates have been measured at 650 degrees C under...... carbon dioxide atmosphere. It is found that the solubilities of NiO and PbO decrease while those of Fe2O3 and Bi2O3 remain approximately constant as the lithium mole fraction increases from 0.43 to 0.62 in the melt. At a fixed composition of the melt, NiO and PbO display both acidic and basic dissolution...

  17. Interaction of Cu(+) with cytosine and formation of i-motif-like C-M(+)-C complexes: alkali versus coinage metals.

    Science.gov (United States)

    Gao, Juehan; Berden, Giel; Rodgers, M T; Oomens, Jos

    2016-03-14

    The Watson-Crick structure of DNA is among the most well-known molecular structures of our time. However, alternative base-pairing motifs are also known to occur, often depending on base sequence, pH, or the presence of cations. Pairing of cytosine (C) bases induced by the sharing of a single proton (C-H(+)-C) may give rise to the so-called i-motif, which occurs primarily in expanded trinucleotide repeats and the telomeric region of DNA, particularly at low pH. At physiological pH, silver cations were recently found to stabilize C dimers in a C-Ag(+)-C structure analogous to the hemiprotonated C-dimer. Here we use infrared ion spectroscopy in combination with density functional theory calculations at the B3LYP/6-311G+(2df,2p) level to show that copper in the 1+ oxidation state induces an analogous formation of C-Cu(+)-C structures. In contrast to protons and these transition metal ions, alkali metal ions induce a different dimer structure, where each ligand coordinates the alkali metal ion in a bidentate fashion in which the N3 and O2 atoms of both cytosine ligands coordinate to the metal ion, sacrificing hydrogen-bonding interactions between the ligands for improved chelation of the metal cation.

  18. Low temperature alkali metal-sulfur batteries. Final report, December 1, 1974-November 30, 1978

    Energy Technology Data Exchange (ETDEWEB)

    Brummer, S.B.; Rauh, R.D.; Abraham, K.M.; Dampier, F.W.; Subrahmanyam, V.; Pearson, G.F.; Surprenant, J.K.; Buzby, J.M.

    1980-03-01

    Work on the development of rechargeable, ambient-temperature Li/sulfur and Li/metal sulfide batteries is reported. The Li/S system has the cathode material dissolved in the electrolyte, as Li/sub 2/S/sub n/. Tetrahydrofuran, 1M LiAsF/sub 6/, is one of the more attractive electrolytes discovered for this cell, since it can dissolve up to approx. 10M S as Li/sub 2/Sn. Despite the oxidative nature of the electrolyte, Li is stable in it and can be electrodeposited from it on battery charge. Cells of the configuration Li 5M S (as Li/sub 2/S/sub n/), THF, 1M LiAsF/sub 6//carbon can be discharged at 50/sup 0/C with a utilization of nearly 1.5e/sup -//S at the C/3 rate. This corresponds to the rate-capacity goal for this battery in its proposed vehicular or load-leveling applications. Further improvements in rate are possible. Rechargeability of 135 cycles of 0.1 e/sup -//S and approx. 45 cycles of 0.5 e/sup -//S was demonstrated. The self-discharge reaction keeps the Li electrode free of electrically isolated dendrites. Ultimate failure on cycling is due to cathode depletion via precipitation of Li/sub 2/S on the anode in a form insoluble in the electrolyte. Attempts to solubilize the Li/sub 2/S by the internal generation of an oxidizing scavenger (e.g., Br/sub 2/) or by addition of Lewis acids have met only with limited success. Cells of configuration Li/THF, 1M LiAsF/sub 6//insoluble metal sulfide were investigated, using the following cathodes: CuS, NiS, SiS/sub 2/, MnS/sub 2/, FeS, and Bi/sub 2/S/sub 3/. Of these, the most promising new material in terms of energy density and rechargeability is CuS. Well over 100 cycles for Li/CuS cells with moderate cathode loadings were demonstrated. CuS compares favorably with TiS/sub 2/ in terms of energy density and rechargeability and is superior in terms of economics. 39 figures, 19 tables.

  19. Comparison of dissociation mechanism between collisionally activated dissociation and charge inversion using alkali metal targets for chlorophenol isomers

    Science.gov (United States)

    Hayakawa, Shigeo; Kawamura, Yoshiaki; Takahashi, Yutaka

    2005-11-01

    Chlorinated aromatic compounds are well-known environmental pollutants whose toxicities depend dramatically on the chlorine substitution pattern, making differentiation of chlorophenol isomers important for environmental analysis. Collisionally activated dissociation (CAD) spectra and charge inversion spectra of ortho-, meta-, and para-chlorophenols (ClC6H4OH) and their partially deuterated forms (ClC6H4OD) were measured using alkali metal targets. The peaks associated with C6H4O+ and C5H5Cl+ ions observed in the CAD spectra result from the loss of HCl and CO fragments, respectively, after the re-arrangement of the hydroxyl hydrogen atom. The peaks associated with C6H4OH- and ClC6H4O- ions observed in the charge inversion spectra result from Cl loss and from hydroxyl bond dissociation, respectively. Isomeric differentiation is possible based on the clear differences observed in the relative intensities of these pairs of peaks. Although the intensities of the peaks associated with C6H4O+ relative to those of C5H5Cl+ in the CAD spectra are independent of the target species, the intensities of the peaks associated with C6H4OH- relative to those of ClC6H4O- in the charge inversion spectra are target dependent. The isomeric dependence of the positive ion distribution patterns in the CAD spectra is proposed to be due to the differences in the rate of the hydrogen atom re-arrangement process. In contrast, the isomeric dependence of the negative ion distribution patterns in the charge inversion spectra is attributed to differences in the bond strength involved in the direct dissociation process in the neutral intermediate species.

  20. Correlated Phases of Weyl Semi-Metals

    Science.gov (United States)

    Wei, Huazhou

    Weyl Semi-Metals are materials whose properties are strongly influenced by spin-orbit couplings. Their description, at low energies, is in terms of non-relativistic linearly dispersing massless fermions. In this thesis, we explore possible of new correlated phases. In particular we focus on excitonic phases due to particle-hole instabilities in chapters 2 and 3, and on superconducting phases from particle-particle instabilities in chapter 4. The range of the interaction plays a crucial role in determining the most stable phase. For particle-hole instabilities, short-range interactions yield eight phases. At stoichiometry, they all require minimum interaction strengths to ensure their emergence. Only one of them, the chiral excitonic insulator(EI) phase, opens a gap at the nodes. It is energetically most favored and is characterized by a complex vectorial order parameter. Also, it is ferromagnetic with the phase of the order parameter determining the direction of the induced net spin polarization's. In contrast long-range interactions can condense a second gapped state namely the Charge Density Wave (CDW). To highlight the physics, we employ the multipole expansion and analyze to leading order. Expanding the interaction potential and the order parameter in spherical harmonics, the gap equation is obtained and analyzed to obtain the minimum interaction strengths linked to phases. We end that the critical coupling for CDW phase is half that of the EI phase. Thus, under the Coulomb interaction, CDW phase is more energetically favorable. In chapter 4, we turn to possible superconducting states induced by particle-particle instabilities. As the energy spectrum has even nodes in the Brillouin zone, both intra-nodal finite-momentum pairing and inter-nodal zero-momentum BCS pairing are allowed. For local attractive interaction the finite momentum pairing state with chiral p-wave symmetry is the most favorable phase at finite carrier density. For chemical potential at the

  1. Use of alkali metal salts to prepare high purity single-walled carbon nanotube solutions and thin films

    Science.gov (United States)

    Ashour, Rakan F.

    Single-walled carbon nanotubes (SWCNTs) display interesting electronic and optical properties desired for many advanced thin film applications, such as transparent conductive electrodes or thin-film transistors. Large-scale production of SWCNTs generally results in polydispersed mixtures of nanotube structures. Since SWCNT electronic character (conducting or semiconducting nature) depends on the nanotube structure, application performance is being held back by this inability to discretely control SWCNT synthesis. Although a number of post-production techniques are able to separate SWCNTs based on electronic character, diameter, or chirality, most still suffer from the disadvantage of high costs of materials, equipment, or labor intensity to be relevant for large-scale production. On the other hand, chromatographic separation has emerged as a method that is compatible with large scale separation of metallic and semiconducting SWCNTs. In this work, SWCNTs, in an aqueous surfactant suspension of sodium dodecyl sulfate (SDS), are separated by their electronic character using a gel chromatography process. Metallic SWCNTs (m-SWCNTs) are collected as initial fractions since they show minimum interaction with the gel medium, whereas, semiconducting SWCNTs (sc- SWCNTs) remain adsorbed to the gel. The process of sc-SWCNT retention in the gel is found to be driven by the packing density of SDS around the SWCNTs. Through a series of separation experiments, it is shown that sc-SWCNTs can be eluted from the gel simply by disturbing the configuration of the SDS/SWCNT micellar structure. This is achieved by either introducing a solution containing a co-surfactant, such as sodium cholate (SC), or solutions of alkali metal ionic salts. Analysis of SWCNT suspensions by optical absorption provides insights into the effect of changing the metal ion (M+ = Li+, Na+, and K+) in the eluting solution. Salts with smaller metal ions (e.g. Li+) require higher concentrations to achieve

  2. Understanding the defect chemistry of alkali metal strontium silicate solid solutions: insights from experiment and theory

    KAUST Repository

    Bayliss, Ryan D.

    2014-09-24

    © the Partner Organisations 2014. Recent reports of remarkably high oxide ion conduction in a new family of strontium silicates have been challenged. It has recently been demonstrated that, in the nominally potassium substituted strontium germanium silicate material, the dominant charge carrier was not the oxygen ion, and furthermore that the material was not single phase (R. D. Bayliss et. al., Energy Environ. Sci., 2014, DOI: 10.1039/c4ee00734d). In this work we re-investigate the sodium-doped strontium silicate material that was reported to exhibit the highest oxide ion conductivity in the solid solution, nominally Sr0.55Na0.45SiO2.775. The results show lower levels of total conductivity than previously reported and sub-micron elemental mapping demonstrates, in a similar manner to that reported for the Sr0.8K0.2Si0.5Ge0.5O2.9 composition, an inhomogeneous chemical distribution correlating with a multiphase material. It is also shown that the conductivity is not related to protonic mobility. A density functional theory computational approach provides a theoretical justification for these new results, related to the high energetic costs associated with oxygen vacancy formation. This journal is

  3. Interaction of Fe-Al-Cr-C with the melt of an alkali metal carbonate

    Science.gov (United States)

    Nikitina, E. V.

    2015-08-01

    The interaction of an Fe-Al-Cr-C (29.5 wt % Fe, 29.35 wt % Cr, 2.56 wt % C, 38.59 wt % Al) alloy with the melt of a lithium, sodium, or potassium carbonate containing 1-5 wt % addition to a salt phase is studied by gravimetry and measuring the corrosion potential and anode polarization curves in the temperature range 500-600°C. As passivators, the substances that decrease the corrosion losses due to hardening and thickening of an oxide film (lithium, sodium, potassium hydroxides) are used. As corrosion stimulators (activators), sodium chloride, fluoride, and sulfate are used. The coalloying of iron with chromium and aluminum results in high corrosion resistance against both frontal (continuous) and local (pitting, intercrystalline) corrosion as a result of formation of chemically resistant and high-adhesion oxide layers with their participation. X-ray diffraction analysis reveals gamma aluminum oxide, spinel (alumochromite) traces, and lithium aluminate at the surface.

  4. CO2 Extraction from Ambient Air Using Alkali-Metal Hydroxide Solutions Derived from Concrete Waste and Steel Slag

    Science.gov (United States)

    Stolaroff, J. K.; Lowry, G. V.; Keith, D. W.

    2003-12-01

    To mitigate global climate change, deep reductions in CO2 emissions are required in the coming decades. Carbon sequestration will play a crucial role in this reduction. Early adoption of carbon sequestration in low-cost niche markets will help develop the technology and experience required for large-scale deployment. One such niche may be the use of alkali metals from industrial waste streams to form carbonate minerals, a safe and stable means of sequestering carbon. In this research, the potential of using two industrial waste streams---concrete and steel slag---for sequestering carbon is assessed. The scheme is outlined as follows: Ca and Mg are leached with water from a finely ground bed of steel slag or concrete. The resulting solution is sprayed through air, capturing CO2 and forming solid carbonates, and collected. The feasibility of this scheme is explored with a combination of experiments, theoretical calculations, cost accounting, and literature review. The dissolution kinetics of steel slag and concrete as a function of particle size and pH is examined. In stirred batch reactors, the majority of Ca which dissolved did so within the first hour, yielding between 50 and 250 (mg; Ca)/(g; slag) and between 10 and 30 (mg; Ca)/(g; concrete). The kinetics of dissolution are thus taken to be sufficiently fast to support the type of scheme described above. As proof-of-concept, further experiments were performed where water was dripped slowly through a stagnant column of slag or concrete and collected at the bottom. Leachate Ca concentrations in the range of 15 mM were achieved --- sufficient to support the scheme. Using basic physical principles and numerical methods, the quantity of CO2 captured by falling droplets is estimated. Proportion of water loss and required pumping energy is similarly estimated. The results indicate that sprays are capable of capturing CO2 from the air and that the water and energy requirements are tractable. An example system for

  5. Capacitance of the double electrical layer on the copper-group metals in molten alkali metal halides

    Science.gov (United States)

    Kirillova, E. V.; Stepanov, V. P.

    2016-08-01

    The electrochemical impedance is measured to study the capacitance of the double electrical layer of metallic Au, Ag, and Cu as a function of potential and temperature in nine molten salts, namely, the chlorides, bromides, and iodides of sodium, potassium, and cesium. The C- E curve of a gold electrode has an additional minimum in the anodic branch. This minimum for silver is less pronounced and is only observed at low ac signal frequencies in cesium halides. The additional minimum is not detected for copper in any salt under study. This phenomenon is explained on the assumption that the adsorption of halide anions on a positively charged electrode surface has a predominantly chemical rather than an electrostatic character. The specific adsorption in this case is accompanied by charge transfer through the interface and the formation of an adsorbent-adsorbate covalent bond.

  6. Synthesis of monomeric and polymeric alkali and alkaline earth metal complexes using a phosphinoselenoic amide ligand in metal coordination sphere

    Indian Academy of Sciences (India)

    Jayeeta Bhattacharjee; Ravi K Kottalanka; Harinath Adimulam; Tarun K Panda

    2014-09-01

    We report the monomeric complexes of magnesium and calcium of composition [M(THF){2-Ph2P(Se)N(CMe3)}2] [M= Mg (3), n = 1 andM = Ca (4), n = 2)] and polymeric complexes of potassium and barium of composition [K(THF)2{Ph2P(Se)N(CMe3)}] (2) and [K(THF)Ba{Ph2P(Se)N(CMe3)}3](5) respectively. The potassium complex 2 was readily prepared by the reaction of potassium bis(trimethylsilyl)amide with phosphinoselenoic amide ligand (1) at ambient temperature. The calcium complex 4 was prepared by two synthetic routes: in the first method, commonly known as salt metathesis reaction, the potassium complex 2 was made to react with alkaline earth metal diiodide at room temperature to afford the corresponding calcium complex. The metal bis(trimethylsilyl)amides were made to react with protic ligand 1 in the second method to eliminate the volatile bis(trimethyl)silyl amine. The magnesium complex 3 and barium complex 5 were prepared only through the first method. Solid-state structures of all the new complexes were established by single crystal X-ray diffraction analysis. The smaller ionic radii of Mg2+ (0.72Å) and Ca2+ (0.99Å) ions form the monomeric complex, whereas the larger ions K+ (1.38Å) and Ba2+ (1.35Å) were found to form onedimensional polymeric complexes with monoanionic ligand 1. Compound 2 serves an example of magnesium complex with a Mg-Se direct bond.

  7. Analyzing relationships between surface perturbations and local chemical reactivity of metal sites: Alkali promotion of O2 dissociation on Ag(111)

    Science.gov (United States)

    Xin, Hongliang; Linic, Suljo

    2016-06-01

    Many commercial heterogeneous catalysts are complex structures that contain metal active sites promoted by multiple additives. Developing fundamental understanding about the impact of these perturbations on the local surface reactivity is crucial for catalyst development and optimization. In this contribution, we develop a general framework for identifying underlying mechanisms that control the changes in the surface reactivity of a metal site (more specifically the adsorbate-surface interactions) upon a perturbation in the local environment. This framework allows us to interpret fairly complex interactions on metal surfaces in terms of specific, physically transparent contributions that can be evaluated independently of each other. We use Cs-promoted dissociation of O2 as an example to illustrate our approach. We concluded that the Cs adsorbate affects the outcome of the chemical reaction through a strong alkali-induced electric field interacting with the static dipole moment of the O2/Ag(111) system.

  8. The Production of Polycyclic Aromatic Hydrocarbon Anions in Inert Gas Matrices Doped with Alkali Metals. Electronic Absorption Spectra of the Pentacene Anion (C22H14(-))

    Science.gov (United States)

    Halasinski, Thomas M.; Hudgins, Douglas M.; Salama, Farid; Allamandola, Louis J.; Mead, Susan (Technical Monitor)

    1999-01-01

    The absorption spectra of pentacene (C22H14) and its radical cation (C22H14(+)) and anion (C22H14(-)) isolated in inert-gas matrices of Ne, Ar, and Kr are reported from the ultraviolet to the near-infrared. The associated vibronic band systems and their spectroscopic assignments are discussed together with the physical and chemical conditions governing ion (and counterion) production in the solid matrix. In particular, the formation of isolated pentacene anions is found to be optimized in matrices doped with alkali metal (Na and K).

  9. Spectrum, radial wave functions, and hyperfine splittings of the Rydberg states in heavy alkali-metal atoms

    Science.gov (United States)

    Sanayei, Ali; Schopohl, Nils

    2016-07-01

    We present numerically accurate calculations of the bound-state spectrum of the highly excited valence electron in the heavy alkali-metal atoms solving the radial Schrödinger eigenvalue problem with a modern spectral collocation method that applies also for a large principal quantum number n ≫1 . As an effective single-particle potential we favor the reputable potential of Marinescu et al. [Phys. Rev. A 49, 982 (1994)], 10.1103/PhysRevA.49.982. Recent quasiclassical calculations of the quantum defect of the valence electron agree for orbital angular momentum l =0 ,1 ,2 ,... overall remarkably well with the results of the numerical calculations, but for the Rydberg states of rubidium and also cesium with l =3 this agreement is less fair. The reason for this anomaly is that in rubidium and cesium the potential acquires for l =3 deep inside the ionic core a second classical region, thus invalidating a standard Wentzel-Kramers-Brillouin (WKB) calculation with two widely spaced turning points. Comparing then our numerical solutions of the radial Schrödinger eigenvalue problem with the uniform analytic WKB approximation of Langer constructed around the remote turning point rn,j ,l (" close=")n -δ0)">+ we observe everywhere a remarkable agreement, apart from a tiny region around the inner turning point rn,j ,l (-). For s states the centrifugal barrier is absent and no inner turning point exists: rn,j ,0 (-)=0 . With the help of an ansatz proposed by Fock we obtain for the s states a second uniform analytic approximation to the radial wave function complementary to the WKB approximation of Langer, which is exact for r →0+ . From the patching condition, that is, for l =0 the Langer and Fock solutions should agree in the intermediate region 0 application we consider recent spectroscopic data for the hyperfine splittings of the isotopes 85Rb and 87Rb and find a remarkable agreement with the predicted scaling relation An,j ,0 (HFS )=const .

  10. Atomic arrangement and electron band structure of Si(1 1 1)-ß-√3 x √3-Bi reconstruction modified by alkali-metal adsorption: ab initio study.

    Science.gov (United States)

    Eremeev, S V; Chukurov, E N; Gruznev, D V; Zotov, A V; Saranin, A A

    2015-08-05

    Using ab initio calculations, atomic structure and electronic properties of Si(1 1 1)[Formula: see text]-Bi surface modified by adsorption of 1/3 monolayer of alkali metals, Li, Na, K, Rb and Cs, have been explored. Upon adsorption of all metals, a similar atomic structure develops at the surface where twisted chained Bi trimers are arranged into a honeycomb network and alkali metal atoms occupy the [Formula: see text] sites in the center of each honeycomb unit. Among other structural characteristics, the greatest variation concerns the relative heights at which alkali metals reside with respect to Bi-trimer layer. Except for Li, the other metals reside higher than Bi layer and their heights increase with atomic number. All adsorbed surface structures display similar electron band structures of which the most essential feature is metallic surface-state band with a giant spin splitting. This electronic property allows one to consider the Si(1 1 1)[Formula: see text]-Bi surfaces modified by alkali metal adsorption as a set of material systems showing promise for spintronic applications.

  11. Atomic arrangement and electron band structure of Si(1 1 1)-ß-\\sqrt{3}\\times \\sqrt{3} -Bi reconstruction modified by alkali-metal adsorption: ab initio study

    Science.gov (United States)

    Eremeev, S. V.; Chukurov, E. N.; Gruznev, D. V.; Zotov, A. V.; Saranin, A. A.

    2015-08-01

    Using ab initio calculations, atomic structure and electronic properties of Si(1 1 1)\\sqrt{3}× \\sqrt{3} -Bi surface modified by adsorption of 1/3 monolayer of alkali metals, Li, Na, K, Rb and Cs, have been explored. Upon adsorption of all metals, a similar atomic structure develops at the surface where twisted chained Bi trimers are arranged into a honeycomb network and alkali metal atoms occupy the {{T}4} sites in the center of each honeycomb unit. Among other structural characteristics, the greatest variation concerns the relative heights at which alkali metals reside with respect to Bi-trimer layer. Except for Li, the other metals reside higher than Bi layer and their heights increase with atomic number. All adsorbed surface structures display similar electron band structures of which the most essential feature is metallic surface-state band with a giant spin splitting. This electronic property allows one to consider the Si(1 1 1)\\sqrt{3}× \\sqrt{3} -Bi surfaces modified by alkali metal adsorption as a set of material systems showing promise for spintronic applications.

  12. Novel Alkali-Metal Coordination in Phenoxides: Powder Diffraction Results on C(6)H(5)OM (M = Li, Na, K, Rb, Cs).

    Science.gov (United States)

    Dinnebier, R. E.; Pink, Maren; Sieler, J.; Stephens, P. W.

    1997-07-30

    We report the ab initio structure solutions of C(6)H(5)OM (M = K, Rb, Cs) by high-resolution powder X-ray diffraction. The compounds, which are of interest for reactions of the Kolbe-Schmitt type, are isostructural. The crystal structures are orthorhombic, space group Pna2(1), Z = 12, with lattice parameters (a, b, c in Å) 14.1003(1), 17.9121(1), and 7.16475(1) for the K compound, 14.4166(2), 18.2028(2), and 7.4009(1) for the Rb compound, and 14.8448(2), 18.5070(2), and 7.6306(1) for the Cs compound. They have a chain structure [M([6])] along the crystallographic c axis. This is a very unusual arrangement in which two different alkali-metal coordination spheres are observed: a distorted octahedron and a 3-fold oxygen coordination. In the latter, the 3-fold-coordinated unsaturated alkali metals additionally show weak interactions with phenyl rings. We also give powder patterns for the compounds with M = Li, Na. The former crystallizes in the monoclinic space group P2(1)/a with lattice parameters a = 22.594 Å, b = 4.7459 Å, c= 10.053 Å, and beta = 97.82 degrees with Z = 8, but no structure solution was possible. The powder pattern for the Na phenolate is in agreement with the earlier single-crystal structure.

  13. The Synthesis and Characterization of Ionic Liquids for Alkali-Metal Batteries and a Novel Electrolyte for Non-Humidified Fuel Cells

    Science.gov (United States)

    Tucker, Telpriore G.

    This thesis focused on physicochemical and electrochemical projects directed towards two electrolyte types: 1) class of ionic liquids serving as electrolytes in the catholyte for alkali-metal ion conduction in batteries and 2) gel membrane for proton conduction in fuel cells; where overall aims were encouraged by the U.S. Department of Energy. Large-scale, sodium-ion batteries are seen as global solutions to providing undisrupted electricity from sustainable, but power-fluctuating, energy production in the near future. Foreseen ideal advantages are lower cost without sacrifice of desired high-energy densities relative to present lithium-ion and lead-acid battery systems. Na/NiCl2 (ZEBRA) and Na/S battery chemistries, suffer from high operation temperature (>300ºC) and safety concerns following major fires consequent of fuel mixing after cell-separator rupturing. Initial interest was utilizing low-melting organic ionic liquid, [EMI+][AlCl 4-], with well-known molten salt, NaAlCl4, to create a low-to-moderate operating temperature version of ZEBRA batteries; which have been subject of prior sodium battery research spanning decades. Isothermal conductivities of these electrolytes revealed a fundamental kinetic problem arisen from "alkali cation-trapping effect" yet relived by heat-ramping >140ºC. Battery testing based on [EMI+][FeCl4 -] with NaAlCl4 functioned exceptional (range 150-180ºC) at an impressive energy efficiency >96%. Newly prepared inorganic ionic liquid, [PBr4+][Al2Br7-]:NaAl2Br 7, melted at 94ºC. NaAl2Br7 exhibited super-ionic conductivity 10-1.75 Scm-1 at 62ºC ensued by solid-state rotator phase transition. Also improved thermal stability when tested to 265ºC and less expensive chemical synthesis. [PBr4 +][Al2Br7-] demonstrated remarkable, ionic decoupling in the liquid-state due to incomplete bromide-ion transfer depicted in NMR measurements. Fuel cells are electrochemical devices generating electrical energy reacting hydrogen/oxygen gases

  14. Mechanics of Metals with Phase Changes

    Energy Technology Data Exchange (ETDEWEB)

    Lashley, J.C.

    2001-01-01

    New experimental data is presented on some exotic metals that exhibit phase changes at cryogenic temperatures. The types of phase changes that were detected in the specific heat data range from martensitic (diffusion less) transitions to superconducting transitions. In addition, the charge density wave (CDW) state in uranium metal was detected in the specific heat. Specific-heat measurements were made in zero-magnetic field using an apparatus capable of obtaining temperatures as low as 0.4 K. Calibration performed on this apparatus, using a single-crystal copper sample, show its accuracy to be 0.50%, while the resolution was better than 0.1%. Our measurements demonstrate that similar high precision and accurate specific-heat measurements can be obtained on milligram-scale samples. In Chapters 2 and 3, specific-heat measurements are presented for the B2 (CsCl structure) alloy AuZn and for {alpha}-uranium (orthorhombic symmetry). The AuZn alloy exhibits a continuous transition at 64.75 K and an entropy of transition of ({Delta}S{sub tr}) 2.02 J K{sup {minus}1} mol{sup {minus}1}. Calculation of the Debye temperature, by extrapolating of the high temperature phase elastic constants to T = 0 K yields a value of 207 K ({+-}2 K), in favorable agreement with the calorimetric value of 219 K ({+-}0.50 K), despite the intervening martensitic transition. Reported results for single-crystal {alpha}-U show a low-temperature limiting {Theta}{sub D} of 256 K ({+-}0.50 K) and four low-temperature anomalies: a superconducting transition below 1 K, an electronic transition at 22 K, and two anomalies at 38 K and at 42 K indicative of the CDW state. In order to continue the study of the actinide series of elements, a program was initiated to first purify and then grow single crystals of plutonium. Accordingly, the focus of Chapters 4 through 6 will be a description of plutonium sample preparation. In this program plutonium metal was purified via zone refining, using a levitated molten

  15. Mechanics of Metals with Phase Changes

    Energy Technology Data Exchange (ETDEWEB)

    Lashley, Jason C. [Brigham Young Univ., Provo, UT (United States)

    2001-01-01

    New experimental data is presented on some exotic metals that exhibit phase changes at cryogenic temperatures. The types of phase changes that were detected in the specific heat data range from martensitic (diffusion less) transitions to superconducting transitions. In addition, the charge density wave (CDW) state in uranium metal was detected in the specific heat. Specific-heat measurements were made in zero-magnetic field using an apparatus capable of obtaining temperatures as low as 0.4 K. Calibration performed on this apparatus, using a single-crystal copper sample, show its accuracy to be 0.50%, while the resolution was better than 0.1%. Our measurements demonstrate that similar high precision and accurate specific-heat measurements can be obtained on milligram-scale samples. In Chapters 2 and 3, specific-heat measurements are presented for the B2 (CsCl structure) alloy AuZn and for α-uranium (orthorhombic symmetry). The AuZn alloy exhibits a continuous transition at 64.75 K and an entropy of transition of (ΔStr) 2.02 J K-1 mol-1. Calculation of the Debye temperature, by extrapolating of the high temperature phase elastic constants to T = 0 K yields a value of 207 K (±2 K), in favorable agreement with the calorimetric value of 219 K (±0.50 K), despite the intervening martensitic transition. Reported results for single-crystal α-U show a low-temperature limiting θD of 256 K (±0.50 K) and four low-temperature anomalies: a superconducting transition below 1 K, an electronic transition at 22 K, and two anomalies at 38 K and at 42 K indicative of the CDW state. In order to continue the study of the actinide series of elements, a program was initiated to first purify and then grow single crystals of plutonium. Accordingly, the focus of Chapters 4 through 6 will be a description of plutonium sample preparation. In this program plutonium metal was purified via zone refining, using a levitated molten zone to minimize

  16. Production of Synthesis Gas via Methane Reforming with CO2 on Ni/SiO2 Catalysts Promoted by Alkali and Alkaline Earth Metals

    Institute of Scientific and Technical Information of China (English)

    陈平; 侯昭胤; 郑小明

    2005-01-01

    Ni/SiO2 catalysts promoted by alkali metals K and Cs or alkaline earth metals Mg, Ca, Sr and Ba were prepared, characterized by H2-TPR and XRD, and used for the production of synthesis gas via methane reforming with CO2. Though K and Cs promoted Ni catalysts could eliminate coke deposition, the reforming activity of these promoted catalysts was decreased heavily. Mg and Ca promoted Ni/SiO2 catalysts exhibited excellent coke resistance ability with minor loss of the reforming activity of Ni/SiO2. Ba showed poor coke resistance ability and small amount of Sr increased the formation of coke. The possible mechanism of these promoters was discussed.

  17. Fragmentation study of rutin, a naturally occurring flavone glycoside cationized with different alkali metal ions, using post-source decay matrix-assisted laser desorption/ionization mass spectrometry.

    Science.gov (United States)

    Kéki, S; Deák, G; Zsuga, M

    2001-12-01

    A post-source decay matrix-assisted laser desorption/ionization mass spectrometric (PSD-MALDI-MS) study of rutin, a naturally occurring flavone glycoside cationized with different alkali metal ions, is reported. The fragmentations of rutin were performed by selecting the [R + Cat]+ peaks for PSD, where R represents a rutin molecule and Cat an alkali metal ion (Li+, Na+, K+). The PSD-MALDI mass spectra showed, depending on Cat, different fragmentation patterns with respect to both the quality and quantity of the fragment ions formed. The intensity of fragmentation decreased in the order Li+ > Na+ > K+. The fragmentation mechanism and an explanation for the observed differences are suggested.

  18. Dispersion C3 coefficients for the alkali-metal atoms interacting with a graphene layer and with a carbon nanotube

    CERN Document Server

    Arora, Bindiya; Sahoo, B K

    2013-01-01

    We evaluate separation dependent van der Waal dispersion ($C_3$) coefficients for the interactions of the Li, Na, K and Rb alkali atoms with a graphene layer and with a single walled carbon nanotube (CNT) using the hydrodynamic and Dirac models. The results from both the models are evaluated using accurate values of the dynamic polarizabilities of the above atoms. Accountability of these accurate values of dynamical polarizabilities of the alkali atoms in determination of the above $C_3$ coefficients are accentuated by comparing them with the coefficients evaluated using the dynamic dipole polarizabilities estimated from the single oscillator approximation which are typically employed in the earlier calculations. For practical description of the atom-surface interaction potentials the radial dependent $C_3$ coefficients are given for a wide range of separation distances between the ground states of the considered atoms and the wall surfaces and also for different values of nanotube radii. The coefficients for...

  19. Structure and composition of the superconducting phase in alkali iron selenide KyFe1.6+xSe2

    Science.gov (United States)

    Carr, Scott V.; Louca, Despina; Siewenie, Joan; Huang, Q.; Wang, Aifeng; Chen, Xianhui; Dai, Pengcheng

    2014-04-01

    We use neutron diffraction to study the temperature evolution of the average structure and local lattice distortions in insulating and superconducting potassium iron selenide KyFe1.6+xSe2. In the high temperature paramagnetic state, both materials have a single phase with a crystal structure similar to that of the BaFe2As2 family of iron pnictides. While the insulating KyFe1.6+xSe2 forms a √5 ×√5 iron vacancy ordered block antiferromagnetic (AF) structure at low temperature, the superconducting compounds spontaneously phase separate into an insulating part with √5 ×√5 iron vacancy order and a superconducting phase with chemical composition of KzFe2Se2 and BaFe2As2 structure. Therefore, superconductivity in alkaline iron selenides arises from alkali deficient KzFe2Se2 in the matrix of the insulating block AF phase.

  20. Two-photon photoemission investigation of electronic and dynamical properties of alkali atoms adsorbed on noble metal surfaces

    Science.gov (United States)

    Sametoglu, Vahit

    We present a systematic time-resolved two-photon photoemission study of the electronic and dynamical properties of Li through Cs adsorbed on Cu(111) and Ag(111) surfaces. A fundamental problem in surface science is how to describe the electronic structure of a chemisorption interface based on the intrinsic properties of the interacting materials. Because of their simple s-electron structure, elements of the alkali atom group comprise paradigmatic adsorbates in many theories of chemisorption, whereas the complementary experimental studies are sparse and incomplete. Through a combination of spectroscopic and femtosecond time-resolved surface measurements, we are able to probe systematically the binding energies, symmetries, and electron and nuclear relaxation dynamics of the initially unoccupied alkali atom resonances. As a prelude, we study the two-photon photoemission process occurring at the bare Ag(111) surface. We develop a quantitative model for two-photon photoemission process, where the nonresonant and k-dependent two-photon absorption between the lower and upper sp-bands is modeled by the optical Bloch equations, and the angle-dependent intensities are described by the Fresnel equations. Our two-photon photoemission spectra of Li through Cs chemisorbed Cu(111) and Ag(111) surfaces reveal two resonances with the m = 0 and m = +/-1 symmetry ('m' is the projection of the orbital angular momentum 'l' onto the surface plane). For the m = 0 resonance, which is derived from the hybridization of the ns and npz orbitals of alkali atoms, we find a binding energy of 1.84--1.99 eV below the vacuum level, which is independent of the alkali atom period, and tunes with coverage in a universal manner. At 0.3--0.7 eV higher energy, we discover and identify the m = +/-1 resonance by its characteristic angular intensity distribution, which derives from the antisymmetry of the npx and npy orbitals. We implement a quantitative model for the alkali atom chemisorption based on the

  1. Gas: A Neglected Phase in Remediation of Metals and Radionuclides

    Energy Technology Data Exchange (ETDEWEB)

    Denham, Miles E.; Looney, Brian B

    2005-09-28

    The gas phase is generally ignored in remediation of metals and radionuclides because it is assumed that there is no efficient way to exploit it. In the literal sense, all remediations involve the gas phase because this phase is linked to the liquid and solid phases by vapor pressure and thermodynamic relationships. Remediation methods that specifically use the gas phase as a central feature have primarily targeted volatile organic contaminants, not metals and radionuclides. Unlike many organic contaminants, the vapor pressure and Henry's Law constants of metals and radionuclides are not generally conducive to direct air stripping of dissolved contaminants. Nevertheless, the gas phase can play an important role in remediation of inorganic contaminants and provide opportunities for efficient, cost effective remediation. The objective here is to explore ways in which manipulation of the gas phase can be used to facilitate remediation of metals and radionuclides.

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

    Science.gov (United States)

    Gilson, Denis F R; Moyer, Ralph O

    2012-02-06

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

  3. Phase Equilibria of Alkali Nitrates (NaNO3, KNO3, RbNO3, CsNO3)in Glycerol + H2O System at Various Temperatures

    OpenAIRE

    Zhang, H.-Y.; Li, S.-N.; Zhai, Q.-G.; Ou, Y.-M.; Jiang, Y.-C.; Hu, M.-C.

    2014-01-01

    By using a homemade research device for phase equilibrium, the equilibrium solubility of the alkali nitrates (NaNO3/KNO3/RbNO3/CsNO3) in the mixed solvent glycerol [HOCH2CH(OH)CH2OH] + H2O in the mass fraction range of glycerol (0.0 to 1.0) at 35 and 45 °C was measured. Moreover, the density and refractive index of the saturated solutions of NaNO3/KNO3/RbNO3/CsNO3 + mixed solvent glycerol + H2O were determined. T...

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

    Science.gov (United States)

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

    2014-12-07

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

  5. Wigner Distribution Functions as a Tool for Studying Gas Phase Alkali Metal Plus Noble Gas Collisions

    Science.gov (United States)

    2014-03-27

    molecular axis, and a transition takes place that changes the electronic projection onto the molecular axis. The Hamiltonian in Eq. 6.2 is in diabatic ...Møller states were calculated using the asymptotic Hamiltonian and the 3 × 3 full Hamiltonian. Because the Hamiltonian is in the diabatic state, the...in the adiabatic basis rather than the diabatic basis. Thus a transformation matrix must be applied to the wavefunction. After the potential operator

  6. Preparation of Cyclic Urethanes from Amino Alcohols and Carbon Dioxide Using Ionic Liquid Catalysts with Alkali Metal Promoters

    Directory of Open Access Journals (Sweden)

    Masahiko Arai

    2006-10-01

    Full Text Available Several ionic liquids were applied as catalysts for the synthesis of cyclicurethanes from amino alcohols and pressurized CO2 in the presence of alkali metalcompounds as promoters. A comparative study was made for the catalytic performanceusing different ionic liquids, substrates, promoters, and pressures. The optimum catalyticsystem was BMIM-Br promoted by K2CO3, which, for 1-amino-2-propanol, produced cyclicurethane in 40% yield with a smaller yield of substituted cyclic urea and no oligomericbyproducts. For other amino alcohols, cyclic urethanes, cyclic ureas, and/or undesiredbyproducts were produced in different yields depending on the substrates used. Possiblereaction mechanisms are proposed.

  7. Purification and Characterization of an Extracellular, Thermo-Alkali-Stable, Metal Tolerant Laccase from Bacillus tequilensis SN4

    OpenAIRE

    Sonica Sondhi; Prince Sharma; Shilpa Saini; Neena Puri; Naveen Gupta

    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 (k cat/K m) showed that 2, 6-dimethoxyphenol was most efficiently oxidized by the enzyme. The enzyme was inhibite...

  8. Quantum-chemistry based calibration of the alkali metal cation series (Li(+)-Cs(+)) for large-scale polarizable molecular mechanics/dynamics simulations.

    Science.gov (United States)

    Dudev, Todor; Devereux, Mike; Meuwly, Markus; Lim, Carmay; Piquemal, Jean-Philip; Gresh, Nohad

    2015-02-15

    The alkali metal cations in the series Li(+)-Cs(+) act as major partners in a diversity of biological processes and in bioinorganic chemistry. In this article, we present the results of their calibration in the context of the SIBFA polarizable molecular mechanics/dynamics procedure. It relies on quantum-chemistry (QC) energy-decomposition analyses of their monoligated complexes with representative O-, N-, S-, and Se- ligands, performed with the aug-cc-pVTZ(-f) basis set at the Hartree-Fock level. Close agreement with QC is obtained for each individual contribution, even though the calibration involves only a limited set of cation-specific parameters. This agreement is preserved in tests on polyligated complexes with four and six O- ligands, water and formamide, indicating the transferability of the procedure. Preliminary extensions to density functional theory calculations are reported.

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

    Science.gov (United States)

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

    2005-09-01

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

  10. Complete Series of Alkali-Metal M(BH3NH2BH2NH2BH3) Hydrogen-Storage Salts Accessed via Metathesis in Organic Solvents.

    Science.gov (United States)

    Owarzany, Rafał; Fijalkowski, Karol J; Jaroń, Tomasz; Leszczyński, Piotr J; Dobrzycki, Łukasz; Cyrański, Michał K; Grochala, Wojciech

    2016-01-04

    We report a new efficient way of synthesizing high-purity hydrogen-rich M(BH3NH2BH2NH2BH3) salts (M = Li, Na, K, Rb, Cs). The solvent-mediated metathetic synthesis applied here uses precursors containing bulky organic cations and weakly coordinating anions. The applicability of this method permits the entire series of alkali-metal M(BH3NH2BH2NH2BH3) salts (M = Li, Na, K, Rb, Cs) to be obtained, thus enabling their comparative analysis in terms of crystal structures and hydrogen-storage properties. A novel polymorphic form of Verkade's base (C18H39N4PH)(BH3NH2BH2NH2BH3) precursor was also characterized structurally. For all compounds, we present a comprehensive structural, spectroscopic, and thermogravimetric characterization (PXRD, NMR, FTIR, Raman, and TGA/DSC/MS).

  11. Volatilisation of alkali and alkaline earth metallic species during the gasification of a Victorian brown coal in CO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Quyn, Dimple Mody; Li, Chun-Zhu [CRC for Clean Power from Lignite, Department of Chemical Engineering, PO Box 36, Monash University, Victoria 3800 (Australia); Hayashi, Jun-ichiro [Centre for Advanced Research of Energy Conversion Materials, Hokkaido University, N13-W8, Kita-ku, Sapporo 060-8628 (Japan)

    2005-08-25

    A Victorian brown coal was gasified in a bench-scale quartz fluidised-bed/fixed-bed reactor in order to study the volatilisation of Na, Ca, and Mg during devolatilisation and gasification and their roles in the reactivity of chars. It was found that the majority of Na was volatilised at 900 {sup o}C under all conditions and that a Na retention limit was achieved in the char with the progress of CO{sub 2} gasification. In some cases, the presence of CO{sub 2} during devolatilisation enhanced the Na retention in the char. In contrast, the retention of Ca (and Mg) was unaffected by CO{sub 2} during devolatilisation at 900C but decreased drastically upon nascent char gasification. The fundamental differences in volatilisation between the alkali and alkaline earth metallic species are discussed in this paper.

  12. The evolution of strength and crystalline phases for alkali-activated ground blast furnace slag and fly ash-based geopolymers

    KAUST Repository

    Oh, Jae Eun

    2010-02-01

    The increase in strength and evolution of crystalline phases in inorganic polymer cement, made by the alkali activation of slag, Class C and Class F fly ashes, was followed using compressive strength test and synchrotron X-ray diffraction. In order to increase the crystallinity of the product the reactions were carried out at 80 °C. We found that hydrotalcite formed in both the alkali-activated slag cements and the fly ash-based geopolymers. Hydroxycancrinite, one member of the ABC-6 family of zeolites, was found only in the fly ash geopolymers. Assuming that the predominantly amorphous geopolymer formed under ambient conditions relates to the crystalline phases found when the mixture is cured at high temperature, we propose that the structure of this zeolitic precursor formed in Na-based high alkaline environment can be regarded as a disordered form of the basic building unit of the ABC-6 group of zeolites which includes poly-types such as hydroxycancrinite, hydroxysodalite and chabazite-Na. © 2009 Elsevier Ltd.

  13. Size-specific interaction of alkali metal ions in the solvation of M+-benzene clusters by Ar atoms.

    Science.gov (United States)

    Huarte-Larrañaga, F; Aguilar, A; Lucas, J M; Albertí, M

    2007-08-23

    The size-specific influence of the M+ alkali ion (M = Li, Na, K, Rb, and Cs) in the solvation process of the M+-benzene clusters by Ar atoms is investigated by means of molecular dynamic simulations. To fully understand the behavior observed in M+-bz-Ar(n) clusters, solvation is also studied in clusters containing either M+ or benzene only. The potential energy surfaces employed are based on a semiempirical bond-atom decomposition, which has been developed previously by some of the authors. The outcome of the dynamics is analyzed by employing radial distribution functions, studying the evolution of the distances between the Ar atoms and the alkali ion M+ or the benzene molecule for all M+-bz-Ar(n) clusters. For all members, in the M+-bz series, the benzene molecule (bz) is found to remain strongly bound to M+ even in the presence of solvent atoms. The radial distribution functions for the heavier clusters (K+-bz, Rb+-bz, and Cs+-bz), are found to be different than for the lighter (Na+-bz and Li+-bz) ones.

  14. QED radiative corrections and many-body effects in atoms: the Uehling potential and shifts in alkali metals

    CERN Document Server

    Ginges, J S M

    2015-01-01

    We consider the largest (Uehling) contribution to the one-loop vacuum polarization correction to the binding energies in neutral alkali atoms, from Na through to the superheavy element E119. We use the relativistic Hartree-Fock method to demonstrate the importance of core relaxation effects. These effects are sizeable everywhere, though particularly important for orbitals with angular momentum quantum number l > 0. For d waves, the Uehling shift is enhanced by many orders of magnitude: for Cs the enhancement is more than four orders of magnitude and for the lighter alkali atoms it is even larger. We also study the effects of second- and higher-order many-body perturbation theory on the valence level shifts through inclusion of the correlation potential. The many-body enhancement mechanisms that operate in the case of the Uehling potential apply also to the case of the larger QED self-energy radiative corrections. The huge enhancement for d level shifts makes high-precision studies of transition frequencies in...

  15. Alkali metal ion catalysis and inhibition in nucleophilic displacement reactions at phosphorus centers: ethyl and methyl paraoxon and ethyl and methyl parathion.

    Science.gov (United States)

    Um, Ik-Hwan; Shin, Young-Hee; Lee, Seung-Eun; Yang, Kiyull; Buncel, Erwin

    2008-02-01

    We report on the ethanolysis of the P=O and P=S compounds ethyl and methyl paraoxon (1a and 1b) and ethyl and methyl parathion (2a and 2b). Plots of spectrophotometrically measured rate constants, kobsd versus [MOEt], the alkali ethoxide concentration, show distinct upward and downward curvatures, pointing to the importance of ion-pairing phenomena and a differential reactivity of free ions and ion pairs. Three types of reactivity and selectivity patterns have been discerned: (1) For the P=O compounds 1a and 1b, LiOEt > NaOEt > KOEt > EtO-; (2) for the P=S compound 2a, KOEt > EtO- > NaOEt > LiOEt; (3) for P=S, 2b, 18C6-crown-complexed KOEt > KOEt = EtO(-) > NaOEt > LiOEt. These selectivity patterns are characteristic of both catalysis and inhibition by alkali-metal cations depending on the nature of the electrophilic center, P=O vs P=S, and the metal cation. Ground-state (GS) vs transition-state (TS) stabilization energies shed light on the catalytic and inhibitory tendencies. The unprecedented catalytic behavior of crowned-K(+) for the reaction of 2b is noteworthy. Modeling reveals an extreme steric interaction for the reaction of 2a with crowned-K(+), which is responsible for the absence of catalysis in this system. Overall, P=O exhibits greater reactivity than P=S, increasing from 50- to 60-fold with free EtO(-) and up to 2000-fold with LiOEt, reflecting an intrinsic P=O vs P=S reactivity difference (thio effect). The origin of reactivity and selectivity differences in these systems is discussed on the basis of competing electrostatic effects and solvational requirements as function of anionic electric field strength and cation size (Eisenman's theory).

  16. sup 29 Si magic angle spinning NMR spectra of alkali metal, alkaline earth metal, and rare earth metal ion exchanged Y zeolites

    Energy Technology Data Exchange (ETDEWEB)

    Chao, Kueijung; Chern, Jeryoung (Tsinghua Univ., Taiwan (China))

    1989-02-23

    The variation of the extraframework cation location in groups IA and IIA metals and rare earth metal (RE) Y zeolites as a function of the dehydration and the rehydration is monitored by {sup 29}Si MAS NMR. Unheated hydrated zeolites give similar {sup 29}Si spectra as they present the similar cation distributions. Upon dehydration a high-field shift is observed which correlates with the distortion of bond angles in silicon-oxygen tetrahedra. The line shapes of {sup 29}Si spectra depend on the nature and the location of the exchangeable cations and the occupancy of the different sites in dehydrated and rehydrated states. The correlation between the line shape of {sup 29}Si spectra and the migration of cations from the supercages to the sodalite cages after heating treatment was studied. The results of {sup 29}Si NMR agree with the known structure data.

  17. Structures of Hydrated Alkali Metal Cations, M+(H2O)nAr (m = Li, Na, K, rb and Cs, n = 3-5), Using Infrared Photodissociation Spectroscopy and Thermodynamic Analysis

    Science.gov (United States)

    Ke, Haochen; van der Linde, Christian; Lisy, James M.

    2014-06-01

    Alkali metal cations play vital roles in chemical and biochemical systems. Lithium is widely used in psychiatric treatment of manic states and bipolar disorder; Sodium and potassium are essential elements, having major biological roles as electrolytes, balancing osmotic pressure on body cells and assisting the electroneurographic signal transmission; Rubidium has seen increasing usage as a supplementation for manic depression and depression treatment; Cesium doped compounds are used as essential catalysts in chemical production and organic synthesis. Since hydrated alkali metal cations are ubiquitous and the basic form of the alkali metal cations in chemical and biochemical systems, their structural and thermodynamic properties serve as the foundation for modeling more complex chemical and biochemical processes, such as ion transport and ion size-selectivity of ionophores and protein channels. By combining mass spectrometry and infrared photodissociation spectroscopy, we have characterized the structures and thermodynamic properties of the hydrated alkali metal cations, i.e. M+(H2O)nAr, (M = Li, Na, K, Rb and Cs, n = 3-5). Ab initio calculations and RRKM-EE (evaporative ensemble) calculations were used to assist in the spectral assignments and thermodynamic analysis. Results showed that the structures of hydrated alkali metal cations were determined predominantly by the competition between non-covalent interactions, i.e. the water---water hydrogen bonding interactions and the water---cation electrostatic interactions. This balance, however, is very delicate and small changes, i.e. different cations, different levels of hydration and different effective temperatures clearly impact the balance.

  18. Mechanisms of diffusional phase transformations in metals and alloys

    CERN Document Server

    Aaronson, Hubert I; Lee, Jong K

    2010-01-01

    Developed by the late metallurgy professor and master experimentalist Hubert I. Aaronson, this collection of lecture notes details the fundamental principles of phase transformations in metals and alloys upon which steel and other metals industries are based. Mechanisms of Diffusional Phase Transformations in Metals and Alloys is devoted to solid-solid phase transformations in which elementary atomic processes are diffusional jumps, and these processes occur in a series of so-called nucleation and growth through interface migration. Instead of relying strictly on a pedagogical approach, it doc

  19. 基于光谱吸收法的碱金属原子配比检测方法研究%Measurement of Mole Ratio for Alkali Metal Mixture by Using Spectral Absorption Method

    Institute of Scientific and Technical Information of China (English)

    邹升; 张红; 陈瑶; 陈熙源

    2015-01-01

    The ratio of alkali metal mixture is one of the most important parameters in gauge head belonging to the ultra‐sensitiv‐ity inertial measurement equipment ,which is required to detect precisely .According to the feature that ratio of alkali metal is re‐lated 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 magni‐tude ,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% .%碱金属混合物原子配比是超高灵敏惯性测量装置表头的重要参数,需精确测量。针对碱金属配比与碱金属蒸汽密度相关的特点,提出运用光深理论检测碱金属配比。结果表明:受多种因素影响,光深理论得到的碱金属蒸汽密度与饱和蒸汽压经验公式计算的结果相差3个数量级,无法保证碱金属配比的测量精度;改变数据处理方法,建立光谱吸收率与气室内部温度的映射模型,运用光谱吸收率标定碱金属气室内部温度,通过碱金属饱和蒸汽压经验公式计算气室内部碱金属原子的配比,多组数据分析表明:检测误差在10%以内。

  20. Alkali-Metal-Mediated Magnesiations of an N-Heterocyclic Carbene: Normal, Abnormal, and "Paranormal" Reactivity in a Single Tritopic Molecule.

    Science.gov (United States)

    Martínez-Martínez, Antonio J; Fuentes, M Ángeles; Hernán-Gómez, Alberto; Hevia, Eva; Kennedy, Alan R; Mulvey, Robert E; O'Hara, Charles T

    2015-11-16

    Herein the sodium alkylmagnesium amide [Na4Mg2(TMP)6(nBu)2] (TMP=2,2,6,6-tetramethylpiperidide), a template base as its deprotonating action is dictated primarily by its 12 atom ring structure, is studied with the common N-heterocyclic carbene (NHC) IPr [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]. Remarkably, magnesiation of IPr occurs at the para-position of an aryl substituent, sodiation occurs at the abnormal C4 position, and a dative bond occurs between normal C2 and sodium, all within a 20 atom ring structure accommodating two IPr(2-). Studies with different K/Mg and Na/Mg bimetallic bases led to two other magnesiated NHC structures containing two or three IPr(-) monoanions bound to Mg through abnormal C4 sites. Synergistic in that magnesiation can only work through alkali-metal mediation, these reactions add magnesium to the small cartel of metals capable of directly metalating a NHC.

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

    Science.gov (United States)

    Kim, Hugh I; Beauchamp, J L

    2008-01-30

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

  2. Structural changes of polyacids initiated by their neutralization with various alkali metal hydroxides. Diffusion studies in poly(acrylic acid)s.

    Science.gov (United States)

    Masiak, Michal; Hyk, Wojciech; Stojek, Zbigniew; Ciszkowska, Malgorzata

    2007-09-27

    The changes in the three-dimensional structure of the poly(acrylic acid), PAA, induced by incorporation of various alkali-metal counterions have been evaluated by studying diffusion of an uncharged probe (1,1'-ferrocenedimethanol) in the polymeric media. The studies are supported by the measurements of conductivity and viscosity of the polymeric media. Solutions of linear PAA of four different sizes (molecular weights: 450,000, 750,000, 1,250,000, 4,000,000) were neutralized with hydroxides of alkali metals of group 1 of the periodic table (Li, Na, K, Rb, Cs) to the desired neutralization degree. The transport properties of the obtained polyacrylates were monitored by measuring the changes in the probe diffusion coefficient during the titration of the polyacids. The probe diffusivity was determined from the steady-state current of the probe voltammetric oxidation at disk microelectrodes. Diffusivity of the probe increases with the increase in the degree of neutralization and with the increase in viscosity. It reaches the maximum value at about 60-80% of the polyacid neutralization. The way the probe diffusion coefficients change is similar in all polyacid solutions and gels. The increase in the size of a metal cation causes, in general, an enhancement in the transport of probe molecules. The biggest differences in the probe diffusivities are between lithium and cesium polyacrylates. The differences between the results obtained for cesium and rubidium are not statistically significant due to lack of good precision of the voltammetric measurements. The measurements of the electric conductivity of polyacrylates and the theoretical predictions supplemented the picture of electrostatic interactions between the polyanionic chains and the metal cations of increasing size. In all instances of the PAAs, the viscosity of the solutions rapidly increases in the 0-60% range of neutralization and then becomes constant in the 60-100% region. With the exception of the shortest

  3. Gas phase metal cluster model systems for heterogeneous catalysis.

    Science.gov (United States)

    Lang, Sandra M; Bernhardt, Thorsten M

    2012-07-14

    Since the advent of intense cluster sources, physical and chemical properties of isolated metal clusters are an active field of research. In particular, gas phase metal clusters represent ideal model systems to gain molecular level insight into the energetics and kinetics of metal-mediated catalytic reactions. Here we summarize experimental reactivity studies as well as investigations of thermal catalytic reaction cycles on small gas phase metal clusters, mostly in relation to the surprising catalytic activity of nanoscale gold particles. A particular emphasis is put on the importance of conceptual insights gained through the study of gas phase model systems. Based on these concepts future perspectives are formulated in terms of variation and optimization of catalytic materials e.g. by utilization of bimetals and metal oxides. Furthermore, the future potential of bio-inspired catalytic material systems are highlighted and technical developments are discussed.

  4. Thermodynamic properties and phase stability of nanocrystalline metals

    Institute of Scientific and Technical Information of China (English)

    SONG Xiaoyan; LI Lingmei; ZHANG Jiuxing

    2006-01-01

    The fundamental thermodynamic functions of enthalpy, entropy, and Gibbs free energy, as functions of the excess free volume at interfaces, temperature, and grain size, have been derived for single-phase metal nanocrystals. The model was applied to predict the thermal features of nano-grain boundaries and the characteristics of phase transformation in nanocrystalline metals, such as the transformation temperature and the critical grain size for phase transformation at a given temperature. The model predictions have been verified by experimental studies on the β-Co (→) α-Co phase transformation in nanocrystalline Co prepared by ball milling.

  5. Analysis of Organic Acids Accumulated in Kochia Scoparia Shoots and Roots by Reverse-phase High Performance Liquid Chromatography Under Salt and Alkali Stress

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Several organic acids accumulated in Kochia Scoparia shoots and roots were studied by means of reverse-phase high performance liquid chromatography with a C18 column. Five types of binary organic acids were separated. The organic acid concentrations were determined in K. Scoparia seedlings stressed by saline (NaCl) and alkaline(NaHCO3) at the same Na + concentration. Concentrations of organic acids are stimulated by alkaline because the cells will adjust their pH values through the accumulation of organic acids, when the environment is basic. The concentrations of oxalic acid and succinic acid are higher than those of other organic acids, including tartaric acid and malic acid, and the concentration of citric acid is the lowest. The concentrations of the organic acids in the roots are higher than those in the shoots under salt(NaCl) stress, but the results are opposite while the roots are under alkali (NaHCO3) stress. This indicates that there are different adaptive strategies for K. Scoparia seedlings in organic acid metabolism under salt and alkali stress.

  6. Dynamic chiral-at-metal stability of tetrakis(d/l-hfc)Ln(III) complexes capped with an alkali metal cation in solution.

    Science.gov (United States)

    Lin, Yiji; Zou, Fang; Wan, Shigang; Ouyang, Jie; Lin, Lirong; Zhang, Hui

    2012-06-14

    Chiral tetrakis(β-diketonate) Ln(III) complexes Δ-[NaLa(d-hfc)(4)(CH(3)CN)] (1) and Λ-[NaLa(l-hfc)(4) (CH(3)CN)] (2) (d/l-hfc(-) = 3-heptafluo-robutylryl-(+)/(-)-camphorate) are a pair of enantiomers and crystallize in the same Sohncke space group (P2(1)2(1)2(1)) with dodecahedral (DD) geometry. Typically positive and negative exciton splitting patterns around 320 nm were observed in the solid-state circular dichroism (CD) spectra of complexes 1 and 2, which indicate that their shell configurational chiralities are Δ and Λ, respectively. The apparent bisignate couplets in the solid-state CD spectra of [CsLn(d-hfc)(4)(H(2)O)] [Ln = La (3), Yb (5)] and [CsLn(l-hfc)(4)(H(2)O)] [Ln = La (4), Yb (6)] show that they are a pair of enantiomers and their absolute configurations are denoted Δ and Λ, respectively. The crystallographic data of 5 reveals that its coordination polyhedron is the square antiprism (SAP) geometry and it undergoes a phase transition from triclinic (α phase, P1) to monoclinic (β phase, C2) upon cooling. The difference between the two phases is brought about by the temperature dependent behaviour of the coordination water molecules, but this did not affect the configurational chirality of the Δ-SAP-[Yb(d-hfc)(4)](-) moiety. Furthermore, time-dependent CD, UV-vis and (19)F NMR were applied to study the solution behavior of these complexes. It was found that the chiral-at-metal stability of the three pairs of complexes is different and affected by both the Ln(3+) and M(+) ion size. The results show that the Cs(+) cation can retain the metal center chirality and stablize the structures of [Ln(d/l-hfc)(4)](-) or the dissociated tris(d/l-hfc)Ln(III) species in solution for a longer time than that of the Na(+) cation, and it is important that the Cs(+) ion successfully lock the configurational chirality around the Yb(3+) center of the complex species in solution. This is reasoned by the short Cs(+)···FC, Cs(+)···O-Yb and Cs(+)···Yb(3

  7. Non-noble metal based catalysts for aqueous phase processing

    NARCIS (Netherlands)

    van Haasterecht, T.

    2015-01-01

    This thesis concerns the evaluation of the potential of supported non-noble metal catalysts in aqueous phase processes for the production hydrogen and oxygenates. The aim of this thesis is to investigate how different factors, especially the nature of the metal, additives and reaction conditions, de

  8. Nanoscale electrodeposition of low-dimensional metal phases and clusters

    Science.gov (United States)

    Staikov, Georgi

    2016-07-01

    The present status of the problem of electrochemical formation of low-dimensional metal phases is reviewed. The progress in this field achieved in the last two decades is discussed on the basis of experimental results obtained in selected electrochemical systems with well defined single crystal substrates. The influence of crystallographic orientation and surface inhomogeneities of foreign substrates on the mechanism of formation and the atomic structure of two-dimensional (2D) metal phases in the underpotential deposition range is considered. The localized electrodeposition of metal nanoclusters on solid state surfaces applying the STM-tip as a nanoelectrode is demonstrated.

  9. Nanoscale electrodeposition of low-dimensional metal phases and clusters.

    Science.gov (United States)

    Staikov, Georgi

    2016-08-01

    The present status of the problem of electrochemical formation of low-dimensional metal phases is reviewed. The progress in this field achieved in the last two decades is discussed on the basis of experimental results obtained in selected electrochemical systems with well defined single crystal substrates. The influence of crystallographic orientation and surface inhomogeneities of foreign substrates on the mechanism of formation and the atomic structure of two-dimensional (2D) metal phases in the underpotential deposition range is considered. The localized electrodeposition of metal nanoclusters on solid state surfaces applying the STM-tip as a nanoelectrode is demonstrated.

  10. Theoretical study on the ground state of the polar alkali-metal-barium molecules: Potential energy curve and permanent dipole moment

    Energy Technology Data Exchange (ETDEWEB)

    Gou, Dezhi; Kuang, Xiaoyu, E-mail: scu-kuang@163.com; Gao, Yufeng; Huo, Dongming [Institute of Atomic and Molecular Physics, Sichuan University, Chengdu 610065 (China)

    2015-01-21

    In this paper, we systematically investigate the electronic structure for the {sup 2}Σ{sup +} ground state of the polar alkali-metal-alkaline-earth-metal molecules BaAlk (Alk = Li, Na, K, Rb, and Cs). Potential energy curves and permanent dipole moments (PDMs) are determined using power quantum chemistry complete active space self-consistent field and multi-reference configuration interaction methods. Basic spectroscopic constants are derived from ro-vibrational bound state calculation. From the calculations, it is shown that BaK, BaRb, and BaCs molecules have moderate values of PDM at the equilibrium bond distance (BaK:1.62 D, BaRb:3.32 D, and BaCs:4.02 D). Besides, the equilibrium bond length (4.93 Å and 5.19 Å) and dissociation energy (0.1825 eV and 0.1817 eV) for the BaRb and BaCs are also obtained.

  11. Theoretical study on the ground state of the polar alkali-metal-barium molecules: Potential energy curve and permanent dipole moment

    Science.gov (United States)

    Gou, Dezhi; Kuang, Xiaoyu; Gao, Yufeng; Huo, Dongming

    2015-01-01

    In this paper, we systematically investigate the electronic structure for the 2Σ+ ground state of the polar alkali-metal-alkaline-earth-metal molecules BaAlk (Alk = Li, Na, K, Rb, and Cs). Potential energy curves and permanent dipole moments (PDMs) are determined using power quantum chemistry complete active space self-consistent field and multi-reference configuration interaction methods. Basic spectroscopic constants are derived from ro-vibrational bound state calculation. From the calculations, it is shown that BaK, BaRb, and BaCs molecules have moderate values of PDM at the equilibrium bond distance (BaK:1.62 D, BaRb:3.32 D, and BaCs:4.02 D). Besides, the equilibrium bond length (4.93 Å and 5.19 Å) and dissociation energy (0.1825 eV and 0.1817 eV) for the BaRb and BaCs are also obtained.

  12. An Improved Red Spectrum of the Methane or T Dwarf SDSS 1624+0029: The Role of the Alkali Metals.

    Science.gov (United States)

    Liebert; Reid; Burrows; Burgasser; Kirkpatrick; Gizis

    2000-04-20

    A Keck II low-resolution spectrum shortward of 1 µm is presented for SDSS 1624+0029, the first field methane or T dwarf discovered in the Sloan Digital Sky Survey. Significant flux is detected down to the spectrum's short-wavelength limit of 6200 Å. The spectrum exhibits a broad absorption feature centered at 7700 Å, which we interpret as the K i lambdalambda7665, 7699 resonance doublet. The observed flux declines shortward of 7000 Å, most likely owing to the red wing of the Na i doublet. Both Cs i doublet lines are detected more strongly than in an earlier red spectrum. Neither Li i absorption nor Halpha emission are detected. An exploratory model fit to the spectrum suggests that the shape of the red spectrum can be primarily accounted for by the broad wings of the K i and Na i doublets. This behavior is consistent with the argument proffered by Burrows, Marley, & Sharp that strong alkali absorption is principally responsible for depressing T dwarf spectra shortward of 1 µm. In particular, there seems no compelling reason at this time to introduce dust or an additional opacity source in the atmosphere of the Sloan object. The width of the K i and strengths of the Cs i lines also indicate that the Sloan object is warmer than Gl 229B.

  13. Phase Equilibria of Alkali Nitrates (NaNO3, KNO3, RbNO3, CsNO3in Glycerol + H2O System at Various Temperatures

    Directory of Open Access Journals (Sweden)

    Zhang, H.-Y.

    2014-05-01

    Full Text Available By using a homemade research device for phase equilibrium, the equilibrium solubility of the alkali nitrates (NaNO3/KNO3/RbNO3/CsNO3 in the mixed solvent glycerol [HOCH2CH(OHCH2OH] + H2O in the mass fraction range of glycerol (0.0 to 1.0 at 35 and 45 °C was measured. Moreover, the density and refractive index of the saturated solutions of NaNO3/KNO3/RbNO3/CsNO3 + mixed solvent glycerol + H2O were determined. The experimental results showed that, in all systems, with the increase of mass fraction of glycerol, the solubility of the salts and the density of the solution decreased, while the refractive index increased gradually. The solubility, refractive index, and density data were fitted by a four-parameter empirical equation.

  14. Binding energy referencing for XPS in alkali metal-based battery materials research (I): Basic model investigations

    Energy Technology Data Exchange (ETDEWEB)

    Oswald, S., E-mail: s.oswald@ifw-dresden.de

    2015-10-01

    Highlights: • We point to a not seriously solved conflict in energy scale referencing of Li metal samples in XPS. • Model experiments at Li-, Na-metal and Li-doped HOPG samples were used to classify the effects. • Binding energy shifts up to 3 eV are observed when the alkaline metal is present in metallic state. • A phenomenological explanation based on an electrostatic interaction is suggested. • Consequences for energy scale correction depending on the kind of surface species are followed. - Abstract: For the investigation of chemical changes in Li- and Na-ion battery electrode systems, X-ray photoelectron spectroscopy (XPS) is a well-accepted method. Charge compensation and referencing of the binding energy (BE) scale is necessary to account for the involved mostly non-conducting species. Motivated by a conflict in energy scale referencing of Li-metal samples discussed earlier by several authors, further clarifying experimental results on several Li containing reference materials are presented and extended by similar experiments for Na. When correlating the peak positions of characteristic chemical species in all the different prepared model sample states, there seems to be a systematic deviation in characteristic binding energies of several eV if lithium is present in its metallic state. Similar results were found for sodium. The observations are furthermore confirmed by the implementation of inert artificial energy reference material, such as implanted argon or deposited gold. The behavior is associated with the high reactivity of metallic lithium and a phenomenological explanation is proposed for the understanding of the observations. Consequences for data interpretation in Li-ion battery research will be discussed for various applications in part (II)

  15. Three-phase metal kinetics in terrestrial invertebrates exposed to high metal concentrations

    Energy Technology Data Exchange (ETDEWEB)

    Laskowski, Ryszard, E-mail: ryszard.laskowski@uj.edu.pl [Institute of Environmental Sciences, Jagiellonian University, Gronostajowa 7, 30-387 Krakow (Poland); Bednarska, Agnieszka J. [Institute of Environmental Sciences, Jagiellonian University, Gronostajowa 7, 30-387 Krakow (Poland); Spurgeon, David; Svendsen, Claus [Centre for Ecology and Hydrology, Maclean Building, Benson Lane, Crowmarsh Gifford, Wallingford, Oxon, OX10 8BB (United Kingdom); Gestel, Cornelis A.M. van [Institute of Ecological Science, Vrije Universiteit, De Boelelaan 1085, 1081 HV Amsterdam (Netherlands)

    2010-08-15

    Models of metal toxicokinetics are critically evaluated using both newly generated data in the NoMiracle project as well as those originating from older studies. The analysis showed that the most frequently used one-compartment two-phase toxicokinetic model, with one assimilation and one elimination rate constant, does not describe correctly certain data sets pertaining particularly to the pattern of assimilation of trace elements. Using nickel toxicokinetics in carabid beetles and earthworms as examples, we showed that Ni in fact exhibits a three-phase kinetics with a short phase of fast metal accumulation immediately after exposure, followed by partial elimination to an equilibrium concentration at a later stage of a metal exposure phase, and by final elimination upon transfer to an uncontaminated food/soil. A similar phenomenon was also found for data on cadmium kinetics in ground beetles and copper kinetics in earthworms in data already published in the literature that was not accounted for in the earlier analysis of the data. The three-phase model suggests that the physiology of controlling body metal concentrations can change shortly after exposure, at least in some cases, by increasing the elimination rate and/or decreasing metal assimilation. Hence, the three-phase model, that allows for different assimilation and/or elimination rates in different phases of exposure to a toxicant, may provide insight into temporal changes in the physiology of metal handling. Consequently, this alternative model should always be tested when describing metal toxicokinetics when temporal patterns of internal metal concentration exhibit an initial 'overshoot' in body metal concentrations.

  16. The Research Progress of Determination Method for Impurities in High Purity Alkali Metal Salt%高纯碱金属盐中杂质测定方法的研究进展

    Institute of Scientific and Technical Information of China (English)

    王晓辉

    2011-01-01

    高纯碱金属盐的纯度对其应用有很大影响,痕量杂质元素含量的严格控制和准确测定非常重要.本文对高纯碱金属盐中的杂质分析方法(原子吸收光谱法、分光光度法、电感耦合等离子体光谱法、电感耦合等离子体质谱法、离子色谱法等)进行了综述.%The purity of high purity alkali metal salt effects the application a lot. The strictly control and accurate determination of trace impurity is very important. The analysis methods (atomic absorption spectrometry, spectrophotometry, ICP-AES, ICP-MS, ion chromatography) for impurities in high purity alkali metal salt are summarized in this paper.

  17. Calculation of Gallium-metal-Arsenic phase diagrams

    Science.gov (United States)

    Scofield, J. D.; Davison, J. E.; Ray, A. E.; Smith, S. R.

    1991-01-01

    Electrical contacts and metallization to GaAs solar cells must survive at high temperatures for several minutes under specific mission scenarios. The determination of which metallizations or alloy systems that are able to withstand extreme thermal excursions with minimum degradation to solar cell performance can be predicted by properly calculated temperature constitution phase diagrams. A method for calculating a ternary diagram and its three constituent binary phase diagrams is briefly outlined and ternary phase diagrams for three Ga-As-X alloy systems are presented. Free energy functions of the liquid and solid phase are approximated by the regular solution theory. Phase diagrams calculated using this method are presented for the Ga-As-Ge and Ga-As-Ag systems.

  18. Solid-solid phase transitions via melting in metals

    Science.gov (United States)

    Pogatscher, S.; Leutenegger, D.; Schawe, J. E. K.; Uggowitzer, P. J.; Löffler, J. F.

    2016-04-01

    Observing solid-solid phase transitions in-situ with sufficient temporal and spatial resolution is a great challenge, and is often only possible via computer simulations or in model systems. Recently, a study of polymeric colloidal particles, where the particles mimic atoms, revealed an intermediate liquid state in the transition from one solid to another. While not yet observed there, this finding suggests that such phenomena may also occur in metals and alloys. Here we present experimental evidence for a solid-solid transition via the formation of a metastable liquid in a `real' atomic system. We observe this transition in a bulk glass-forming metallic system in-situ using fast differential scanning calorimetry. We investigate the corresponding transformation kinetics and discuss the underlying thermodynamics. The mechanism is likely to be a feature of many metallic glasses and metals in general, and may provide further insight into phase transition theory.

  19. Photoionization in alkali lasers.

    Science.gov (United States)

    Knize, R J; Zhdanov, B V; Shaffer, M K

    2011-04-11

    We have calculated photoionization rates in alkali lasers. The photoionization of alkali atoms in the gain medium of alkali lasers can significantly degrade the laser performance by reducing the neutral alkali density and with it the gain. For a ten atmosphere Rb laser and a Cs exciplex laser, the photoionization induced alkali atom loss rates are greater than 10(5) sec(-1). These high loss rates will quickly deplete the neutral alkali density, reducing gain, and may require fast, possibly, supersonic flow rates to sufficiently replenish the neutral medium for CW operation.

  20. Vacancy defects and defect clusters in alkali metal ion-doped MgO nanocrystallites studied by positron annihilation and photoluminescence spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Sellaiyan, S.; Uedono, A. [University of Tsukuba, Division of Applied Physics, Tsukuba, Ibaraki (Japan); Sivaji, K.; Janet Priscilla, S. [University of Madras, Department of Nuclear Physics, Chennai (India); Sivasankari, J. [Anna University, Department of Physics, Chennai (India); Selvalakshmi, T. [National Institute of Technology, Nanomaterials Laboratory, Department of Physics, Tiruchirappalli (India)

    2016-10-15

    Pure and alkali metal ion (Li, Na, and K)-doped MgO nanocrystallites synthesized by solution combustion technique have been studied by positron lifetime and Doppler broadening spectroscopy methods. Positron lifetime analysis exhibits four characteristic lifetime components for all the samples. Doping reduces the Mg vacancy after annealing to 800 C. It was observed that Li ion migrates to the vacancy site to recover Mg vacancy-type defects, reducing cluster vacancies and micropores. For Na- and K-doped MgO, the aforementioned defects are reduced and immobile at 800 C. Coincidence Doppler broadening studies show the positron trapping sites as vacancy clusters. The decrease in the S parameter is due to the particle growth and reduction in the defect concentration at 800 C. Photoluminescence study shows an emission peak at 445 nm and 498 nm, associated with F{sub 2} {sup 2+} and recombination of higher-order vacancy complexes. Further, annealing process is likely to dissociate F{sub 2} {sup 2+} to F{sup +} and this F{sup +} is converted into F centers at 416 nm. (orig.)

  1. Structures and heats of formation of simple alkali metal compounds: hydrides, chlorides, fluorides, hydroxides, and oxides for Li, Na, and K.

    Science.gov (United States)

    Vasiliu, Monica; Li, Shenggang; Peterson, Kirk A; Feller, David; Gole, James L; Dixon, David A

    2010-04-01

    Geometry parameters, frequencies, heats of formation, and bond dissociation energies are predicted for simple alkali metal compounds (hydrides, chlorides, fluorides, hydroxides and oxides) of Li, Na, and K from coupled cluster theory [CCSD(T)] calculations including core-valence correlation with the aug-cc-pwCVnZ basis set (n = D, T, Q, and 5). To accurately calculate the heats of formation, the following additional correction were included: scalar relativistic effects, atomic spin-orbit effects, and vibrational zero-point energies. For calibration purposes, the properties of some of the lithium compounds were predicted with iterative triple and quadruple excitations via CCSDT and CCSDTQ. The calculated geometry parameters, frequencies, heats of formation, and bond dissociation energies were compared with all available experimental measurements and are in excellent agreement with high-quality experimental data. High-level calculations are required to correctly predict that K(2)O is linear and that the ground state of KO is (2)Sigma(+), not (2)Pi, as in LiO and NaO. This reliable and consistent set of calculated thermodynamic data is appropriate for use in combustion and atmospheric simulations.

  2. First principles study of structural, electronic and mechanical properties of alkali nitride-KN

    Energy Technology Data Exchange (ETDEWEB)

    Murugan, A.; Rajeswarapalanichamy, R., E-mail: rrpalanichamy@gmail.com; Santhosh, M. [Department of Physics, N.M.S.S.V.N college, Madurai, Tamilnadu-625019 (India); Iyakutti, K. [Department of Physics and Nanotechnology, SRM University, Chennai, Tamilnadu-603203 (India)

    2015-06-24

    The structural, electronic and elastic properties of alkali- metal nitride (KN) is investigated by the first principles calculations based on density functional theory as implemented in Vienna ab-initio simulation package. At ambient pressure KN is stable in the ferromagnetic state with NaCl structure. The calculated lattice parameters are in good agreement with the available results. The electronic structure reveals that the KN is half metallic ferromagnet at normal pressure. A pressure-induced structural phase transition from NaCl to ZB phase is observed in KN. Half metallicity and ferromagnetism is maintained at all pressures.

  3. A superconductor to superfluid phase transition in liquid metallic hydrogen.

    Science.gov (United States)

    Babaev, Egor; Sudbø, Asle; Ashcroft, N W

    2004-10-07

    Although hydrogen is the simplest of atoms, it does not form the simplest of solids or liquids. Quantum effects in these phases are considerable (a consequence of the light proton mass) and they have a demonstrable and often puzzling influence on many physical properties, including spatial order. To date, the structure of dense hydrogen remains experimentally elusive. Recent studies of the melting curve of hydrogen indicate that at high (but experimentally accessible) pressures, compressed hydrogen will adopt a liquid state, even at low temperatures. In reaching this phase, hydrogen is also projected to pass through an insulator-to-metal transition. This raises the possibility of new state of matter: a near ground-state liquid metal, and its ordered states in the quantum domain. Ordered quantum fluids are traditionally categorized as superconductors or superfluids; these respective systems feature dissipationless electrical currents or mass flow. Here we report a topological analysis of the projected phase of liquid metallic hydrogen, finding that it may represent a new type of ordered quantum fluid. Specifically, we show that liquid metallic hydrogen cannot be categorized exclusively as a superconductor or superfluid. We predict that, in the presence of a magnetic field, liquid metallic hydrogen will exhibit several phase transitions to ordered states, ranging from superconductors to superfluids.

  4. Experimental Two-Phase Liquid-Metal Magnetohydrodynamic Generator Program

    Science.gov (United States)

    1979-04-01

    efficiencies in excess of 0.8 are attainable. Initial measurements of local flow parameters in a NaK -nitrogen two-phase liquid - metal MHD generator...hot liquid metals . Thus, the concept of using surface-active aaents in MHD generators can be evaluated more rapidly and inexpensively with NaK , the...describe this aggregation of bchbles as a foam. When the Ba- NaK solution was transferred, helium was blown under the surface of the liquid metal with the

  5. Reversible metal-hydride phase transformation in epitaxial films.

    Science.gov (United States)

    Roytburd, Alexander L; Boyerinas, Brad M; Bruck, Hugh A

    2015-03-11

    Metal-hydride phase transformations in solids commonly proceed with hysteresis. The extrinsic component of hysteresis is the result of the dissipation of energy of internal stress due to plastic deformation and fracture. It can be mitigated on the nanoscale, where plastic deformation and fracture are suppressed and the transformation proceeds through formation and evolution of coherent phases. However, the phase coherency introduces intrinsic thermodynamic hysteresis, preventing reversible transformation. In this paper, it is shown that thermodynamic hysteresis of coherent metal-hydride transformation can be eliminated in epitaxial film due to substrate constraint. Film-substrate interaction leads to formation of heterophase polydomain nanostructure with variable phase fraction which can change reversibly by varying temperature in a closed system or chemical potential in an open system.

  6. Evidence for [18-Crown-6 Na]2[S2O4] in methanol and dissociation to Na2S2O4 and 18-Crown-6 in the solid state; accounting for the scarcity of simple oxy dianion salts of alkali metal crown ethers in the solid state.

    Science.gov (United States)

    Bruna, Pablo J; Greer, Scott; Passmore, Jack; Rautiainen, J Mikko

    2011-02-21

    [18-Crown-6 Na](2)S(2)O(4) complex was prepared in methanol solution but dissociates into 18-Crown-6 ((s)) and Na(2)S(2)O(4 (s)) on removal of the solvent. Evidence for complexation in methanol is supported by a quantitative mass analysis and the dissociation in the solid state by vibrational spectroscopy and powder X-ray diffraction. These observations are accounted for by investigating the energetics of complexation in solution and dissociation in the solid state using calculated density functional theory (DFT) gas phase binding enthalpies and free energies combined with conductor-like screening model (COSMO) solvation energies and lattice enthalpy and free energy terms derived from volume based thermodynamics (VBT). Our calculations show that complexation of alkali metal dianion salts to crown ethers are much less favorable than that of the corresponding monoanion salts in the solid state and that the formation of alkali metal crown complexes of stable simple oxy-dianion (e.g., CO(3)(2-), SO(4)(2-)) salts is unlikely. The roles of complexation with 18-Crown-6 and ion pair formation in the process of dissolution of Na(2)S(2)O(4) to methanol are discussed.

  7. Crystal structures and hydrogen bonding in the isotypic series of hydrated alkali metal (K, Rb and Cs complexes with 4-aminophenylarsonic acid

    Directory of Open Access Journals (Sweden)

    Graham Smith

    2017-02-01

    Full Text Available The structures of the alkali metal (K, Rb and Cs complex salts with 4-aminophenylarsonic acid (p-arsanilic acid manifest an isotypic series with the general formula [M2(C6H7AsNO32(H2O3], with M = K {poly[di-μ3-4-aminophenylarsonato-tri-μ2-aqua-dipotassium], [K2(C6H7AsNO32(H2O3], (I}, Rb {poly[di-μ3-4-aminophenylarsonato-tri-μ2-aqua-dirubidium], [Rb2(C6H7AsNO32(H2O3], (II}, and Cs {poly[di-μ3-4-aminophenylarsonato-tri-μ2-aqua-dirubidium], [Cs2(C6H7AsNO32(H2O3], (III}, in which the repeating structural units lie across crystallographic mirror planes containing two independent and different metal cations and a bridging water molecule, with the two hydrogen p-arsanilate ligands and the second water molecule lying outside the mirror plane. The bonding about the two metal cations in all complexes is similar, one five-coordinate, the other progressing from five-coordinate in (I to eight-coordinate in both (II and (III, with overall M—O bond-length ranges of 2.694 (5–3.009 (7 (K, 2.818 (4–3.246 (4 (Rb and 2.961 (9–3.400 (10 Å (Cs. The additional three bonds in (II and (III are the result of inter-metal bridging through the water ligands. Two-dimensional coordination polymeric structures with the layers lying parallel to (100 are generated through a number of bridging bonds involving the water molecules (including hydrogen-bonding interactions, as well as through the arsanilate O atoms. These layers are linked across [100] through amine N—H...O hydrogen bonds to arsonate and water O-atom acceptors, giving overall three-dimensional network structures.

  8. Milk-alkali syndrome

    Science.gov (United States)

    ... this page: //medlineplus.gov/ency/article/000332.htm Milk-alkali syndrome To use the sharing features on this page, please enable JavaScript. Milk-alkali syndrome is a condition in which there ...

  9. Spectroscopic (FT-IR, FT-Raman, UV) and microbiological studies of di-substituted benzoates of alkali metals

    Science.gov (United States)

    Kalinowska, M.; Świsłocka, R.; Borawska, M.; Piekut, J.; Lewandowski, W.

    2008-06-01

    The FT-IR, FT-Raman and UV spectra of 3,5-dihydroxybenzoic and 3,5-dichlorobenzoic acids as well as lithium, sodium, potassium, rubidium, caesium 3,5-dihydroxy- and 3,5-dichlorobenzoates were recorded, assigned and compared. The theoretical geometries, Mulliken atomic charges, IR wavenumbers were obtained in B3LYP/6-311++G** level. On the basis of the gathered experimental and theoretical data the effect of metals and substituents on the electronic system of studied compounds were investigated. Moreover, the antimicrobiological activity of studied compounds against two species of bacteria: Bacillus subtilis, Staphylococus aureus and one species of yeast: Candida albicans were studied after 24 and 48 h of incubation. The attempt was made, to find out whether there is any correlation between the first principal component and the degree of growth inhibition exhibited by studied compounds in relation to selected microorganisms.

  10. Study of structural and spectroscopic behavior of Sm3+ ions in lead-zinc borate glasses containing alkali metal ions

    Science.gov (United States)

    Sasi Kumar, M. V.; Babu, S.; Rajeswara Reddy, B.; Ratnakaram, Y. C.

    2017-02-01

    High luminescence behavior of rare earth inorganic glasses have a variety of uses in the industry. In the past few decades, rare earth ions with characteristic photonics applications are being hosted by heavy metal oxide glasses. Among the rare earth ions Sm3+ ion has features which make it apt for high density optical storage. The authors of the paper have experimented to synthesize Sm3+ doped glasses. In this regard a new series of borate glasses doped with 1 mol% Sm3+ ion are developed by using melt-quenching technique. XRD, FTIR, optical absorption, luminescence techniques are used to study the various characteristics of Sm3+ ion in the present glass matrices. The XRD spectra confirms the amorphous nature of glasses. Further, the researchers have used differential thermal analysis to study the glass transition temperature. The structural groups in the prepared glasses are studied using Fourier transform infrared spectra. From the measurement of its optical absorption, three phenomenological Judd-Ofelt intensity parameters (Ω2, Ω4 and Ω6) have been computed. Based on these Judd-Ofelt intensity parameters, radiative properties such as radiative probabilities (Arad), branching ratios (β), and radiative life time (τR) are calculated. The excitation spectra of Sm3+ doped lithium heavy metal borate glass matrix is recorded under the emission wavelength of 600 nm. The emission spectra are recorded under 404 nm excitation wavelength. From various emission transitions, 4G5/2 → 6H7/2 and 4G5/2 → 6H9/2 bands could be of interest for various applications. The decay profiles of 4G5/2 level exhibit single exponential nature in all the prepared glass matrices. The potassium glass matrix exhibits higher quantum efficiency than the other glass matrices. Finally, by going through these several spectroscopic characterizations, it is concluded that the prepared Sm3+ doped lead-zinc borate glasses might be useful for visible light applications.

  11. Kondo Screening and Fermi Surface in the Antiferromagnetic Metal Phase

    Science.gov (United States)

    Yamamoto, Seiji; Si, Qimiao

    2006-03-01

    We address the Kondo effect deep inside the antiferromagnetic metal phase of a Kondo lattice Hamiltonian with SU(2) invariance. The local- moment component is described in terms of a non-linear sigma model. The Fermi surface of the conduction electron component is taken to be sufficiently small, so that it is not spanned by the antiferromagnetic wavevector. The effective low energy form of the Kondo coupling simplifies drastically, corresponding to the uniform component of the magnetization that forward-scatters the conduction electrons on their own Fermi surface. We use a combined bosonic and fermionic (Shankar) renormalization group procedure to analyze this effective theory and study the Kondo screening and Fermi surface in the antiferromagnetic phase. The implications for the global magnetic phase diagram, as well as quantum critical points, of heavy fermion metals are discussed.

  12. EPR, ELDOR, and ENDOR studies of alkali metal- o-dimesitoylbenzene radical complexes in solution. II. The lithium and sodium complexes

    Science.gov (United States)

    van der Drift, E.; Smidt, J.

    A combined EPR-ELDOR-ENDOR study on ion pairs of o-dimesitoylbenzene anions with Li or Na cations provides a unique description of the alkali relaxation pattern in terms of dipolar and quadrupolar relaxation resulting from molecular tumbling. Internal motions in the chelating ring structure appear to be of minor importance. From the EPR and ELDOR results a variety of structural information is obtained: spectral densities, rotational correlation time of the complex, and anisotropic magnetic interactions of the alkali nucleus.

  13. Elastic phase transitions in metals at high pressures.

    Science.gov (United States)

    Krasilnikov, O M; Vekilov, Yu Kh; Mosyagin, I Yu; Isaev, E I; Bondarenko, N G

    2012-04-19

    The elastic phase transitions of cubic metals at high pressures are investigated within the framework of Landau theory. It is shown that at pressures comparable with the magnitude of the bulk modulus the phase transition is connected with the loss of stability relative to uniform deformation of the crystalline lattice. Discontinuity of the order parameter at the transition point and its equilibrium value are expressed through the second- to fourth-order elastic constants. The second-,third- and fourth-order elastic constants and phonon dispersion curves of vanadium under hydrostatic pressure are obtained by first-principles calculations. Structural transformation in vanadium under pressure is studied using the obtained results. It is shown that the experimentally observed at P ≈ 69 GPa phase transition in vanadium is the first-order phase transition close to a second-order phase transition.

  14. Influence of Filler Metals in Welding Wires on the Phase and Chemical Composition of Weld Metal

    Science.gov (United States)

    Kozyrev, N. A.; Osetkovskiy, I. V.; Kozyreva, O. A.; Zernin, E. A.; Kartsev, D. S.

    2016-04-01

    The influence of filler metals used in welding wires on the phase and chemical composition of the metal, which is surfaced to mining equipment exposed to abrasive wear, has been investigated. Under a laboratory environment, samples of Mo-V-B and Cr-Mn-Mo-V wires were made. The performed experiments have revealed that fillers of the Cr-Mn-Mo-V system used in powder wire show better wear resistance of the weld metal than that of the Mn-Mo-V-B system; the absence of boron, which promotes grain refinement in the Mn-Mo-V-B system, significantly reduces wear resistance; the Mn-Mo-V-B weld metal has a finer structure than the Cr-Mn-Mo-V weld metal.

  15. Orbital disproportionation of electronic density is a universal feature of alkali-doped fullerides

    Science.gov (United States)

    Iwahara, Naoya; Chibotaru, Liviu F.

    2016-10-01

    Alkali-doped fullerides show a wide range of electronic phases in function of alkali atoms and the degree of doping. Although the presence of strong electron correlations is well established, recent investigations also give evidence for dynamical Jahn-Teller instability in the insulating and the metallic trivalent fullerides. In this work, to reveal the interplay of these interactions in fullerides with even electrons, we address the electronic phase of tetravalent fulleride with accurate many-body calculations within a realistic electronic model including all basic interactions extracted from first principles. We find that the Jahn-Teller instability is always realized in these materials too. In sharp contrast to the correlated metals, tetravalent system displays uncorrelated band-insulating state despite similar interactions present in both fullerides. Our results show that the Jahn-Teller instability and the accompanying orbital disproportionation of electronic density in the degenerate lowest unoccupied molecular orbital band is a universal feature of fullerides.

  16. Partitioning of metals in different binding phases of tropical estuarine sediments: importance of metal chemistry.

    Science.gov (United States)

    Chakraborty, Parthasarathi; Chakraborty, Sucharita; Vudamala, Krushna; Sarkar, Arindam; Nath, B Nagender

    2016-02-01

    Distribution of metals in different binding phases of estuarine sediments provides chemically significant description of metal-sediment interactions. This study describes the influences of ligand field stabilization energy (LFSE), Jahn-Teller effect, and water exchange rate (k-w) on metal distribution in different binding phases of estuarine sediments. It was found that Cu had highest affinity for organic binding phases in the studied sediments followed by Ni and Pb. However, Pb showed strong association with Fe/Mn oxide phases followed by Ni and Cu. Faster k-w of Cu (II) (1 × 10(9) s(-1)) increased the rate of complex formation of Cu(2+) ion with ligand in the organic phases. The Cu-ligand (from organic phase) complexes gained extra stability by the Jahn-Teller effect. The combined effects of these two phenomena and high ionic potential increased the association of Cu with the organic phases of the sediments than Ni and Pb. The smaller ionic radii of Ni(2+) (0.72 Å) than Pb(2+) (1.20 Å) increase the stability of Ni-ligand complexes in the organic phase of the sediments. High LFSE of Ni(II) (compared with Pb(2+) ions) also make Ni-organic complexes increasingly stable than Pb. High k-w (7 × 10(9) s(-1)) of Pb did not help it to associate with organic phases in the sediments. The high concentration of Pb in the Fe/Mn oxyhydroxide binding phase was probably due to co-precipitation of Pb(2+) and Fe(3+). High surface area or site availability for Pb(2+) ion on Fe oxyhydroxide phase was probably responsible for the high concentration of Pb in Fe/Mn oxyhydroxide phase. Increasing concentrations of Cu in organic phases with the increasing Cu loading suggest that enough binding sites were available for Cu in the organic binding phases of the sediments. This study also describes the influence of nature of sedimentary organic carbon (terrestrial and marine derived OC) in controlling these metal distribution and speciation in marine sediment.

  17. Controllable formation of heterotrimetallic coordination compounds: systematically incorporating lanthanide and alkali metal ions into the manganese 12-metallacrown-4 framework.

    Science.gov (United States)

    Azar, Michael R; Boron, Thaddeus T; Lutter, Jacob C; Daly, Connor I; Zegalia, Kelcie A; Nimthong, Ruthairat; Ferrence, Gregory M; Zeller, Matthias; Kampf, Jeff W; Pecoraro, Vincent L; Zaleski, Curtis M

    2014-02-01

    structures available through the metallacrown analogy, these complexes allow for the mixing and matching of a diverse range of metals that might permit the fine-tuning of molecular properties where one day they may be exploited as magnetic materials or luminescent agents.

  18. Gas-phase synthesis of magnetic metal/polymer nanocomposites.

    Science.gov (United States)

    Starsich, Fabian H L; Hirt, Ann M; Stark, Wendelin J; Grass, Robert N

    2014-12-19

    Highly magnetic metal Co nanoparticles were produced via reducing flame spray pyrolysis, and directly coated with an epoxy polymer in flight. The polymer content in the samples varied between 14 and 56 wt% of nominal content. A homogenous dispersion of Co nanoparticles in the resulting nanocomposites was visualized by electron microscopy. The size and crystallinity of the metallic fillers was not affected by the polymer, as shown by XRD and magnetic hysteresis measurements. The good control of the polymer content in the product nanocomposite was shown by elemental analysis. Further, the successful polymerization in the gas phase was demonstrated by electron microscopy and size measurements. The presented effective, dry and scalable one-step synthesis method for highly magnetic metal nanoparticle/polymer composites presented here may drastically decrease production costs and increase industrial yields.

  19. Gas-phase synthesis of magnetic metal/polymer nanocomposites

    Science.gov (United States)

    Starsich, Fabian H. L.; Hirt, Ann M.; Stark, Wendelin J.; Grass, Robert N.

    2014-12-01

    Highly magnetic metal Co nanoparticles were produced via reducing flame spray pyrolysis, and directly coated with an epoxy polymer in flight. The polymer content in the samples varied between 14 and 56 wt% of nominal content. A homogenous dispersion of Co nanoparticles in the resulting nanocomposites was visualized by electron microscopy. The size and crystallinity of the metallic fillers was not affected by the polymer, as shown by XRD and magnetic hysteresis measurements. The good control of the polymer content in the product nanocomposite was shown by elemental analysis. Further, the successful polymerization in the gas phase was demonstrated by electron microscopy and size measurements. The presented effective, dry and scalable one-step synthesis method for highly magnetic metal nanoparticle/polymer composites presented here may drastically decrease production costs and increase industrial yields.

  20. Thermodynamic properties of stable and metastable phases of Pt metal

    Institute of Scientific and Technical Information of China (English)

    PENG Hong-jian; XIE You-qing; NIE Yao-zhuang

    2009-01-01

    Isometric heat capacity cv and isobaric heat capacity cp of Pt with stable and metastable phases were calculated by using pure element systematic theory. These results are in excellent agreement with of SGTE (Scientific Group Thermodata Europe) database and JANAF (Joint Army-Navy-Air Force) experimental values. The calculation results of cv and cp of Pt metal in natural state are in good agreement with those calculated by FP(first-principles) method. It is found that the electron devotion to heat capacity is important to adjust in OA(one-atom) method while calculating heat capacity. The full information about thermodynamic properties of Pt metal with stable and metastable phases, such as entropy(S), enthalpy(H) and Gibbs energy(G) were calculated from 0 K to random temperature. The results are in good agreement with JANAF experimental value. In contrast to SGTE database, the thermodynamic properties from 0 K to 298.15 K are implemented.

  1. Phase Behaviors in Bi-phase Simulation of Powder Segregation in Metal Injection Molding

    Institute of Scientific and Technical Information of China (English)

    Liu Baosheng; Fan Xiaoxin; Cheng Zhiqiang

    2006-01-01

    Powder segregation induced by mold filling is an important phenomenon that affects the final quality of metal injection molding (MIM). The prediction of segregation in MIM requires a bi-phase flow model to describe distinctly the flows of metallic powder and polymer binder. Viscous behaviors for the flows of each phase should hence be determined. The coefficient of interaction between the flows of two phases should also be evaluated. However, only viscosity of the mixed feedstock is measurable by capillary tests. Wall sticking is supposed in the traditional model for capillary tests, while the wall slip is important to be taken into account in MIM injection. Objective of the present paper is to introduce the slip effect in bi-phase simulation, and search the suitable way to determine the viscous behaviors for each phase with the consideration of wall slip in capillary tests. Analytical and numerical methods were proposed to realize such a specific purpose. The proposed method is based on the mass conservation between the capillary flows in mono-phase model for the mixed feedstock and in bi-phase model for the flows of two phases. Examples of the bi-phase simulation in MIM were realized with the software developed by research team. The results show evident segregation, which is valuable for improving the mould designs.

  2. On the thermodynamics of phase transitions in metal hydrides

    Science.gov (United States)

    Vita, Andrea

    2012-02-01

    Metal hydrides are solutions of hydrogen in a metal, where phase transitions may occur depending on temperature, pressure etc. We apply Le Chatelier's principle of thermodynamics to a particular phase transition in TiHx, which can approximately be described as a second-order phase transition. We show that the fluctuations of the order parameter correspond to fluctuations both of the density of H+ ions and of the distance between adjacent H+ ions. Moreover, as the system approaches the transition and the correlation radius increases, we show -with the help of statistical mechanics-that the statistical weight of modes involving a large number of H+ ions (`collective modes') increases sharply, in spite of the fact that the Boltzmann factor of each collective mode is exponentially small. As a result, the interaction of the H+ ions with collective modes makes a tiny suprathermal fraction of the H+ population appear. Our results hold for similar transitions in metal deuterides, too. A violation of an -insofar undisputed-upper bound on hydrogen loading follows.

  3. Site Preference in Multimetallic Nanoclusters: Incorporation of Alkali Metal Ions or Copper Atoms into the Alkynyl-Protected Body-Centered Cubic Cluster [Au7 Ag8 (C≡C(t) Bu)12 ]().

    Science.gov (United States)

    Wang, Yu; Su, Haifeng; Ren, Liting; Malola, Sami; Lin, Shuichao; Teo, Boon K; Häkkinen, Hannu; Zheng, Nanfeng

    2016-11-21

    The synthesis, structure, substitution chemistry, and optical properties of the gold-centered cubic monocationic cluster [Au@Ag8 @Au6 (C≡C(t) Bu)12 ](+) are reported. The metal framework of this cluster can be described as a fragment of a body-centered cubic (bcc) lattice with the silver and gold atoms occupying the vertices and the body center of the cube, respectively. The incorporation of alkali metal atoms gave rise to [Mn Ag8-n Au7 (C≡C(t) Bu)12 ](+) clusters (n=1 for M=Na, K, Rb, Cs and n=2 for M=K, Rb), with the alkali metal ion(s) presumably occupying the vertex site(s), whereas the incorporation of copper atoms produced [Cun Ag8 Au7-n (C≡C(t) Bu)12 ](+) clusters (n=1-6), with the Cu atom(s) presumably occupying the capping site(s). The parent cluster exhibited strong emission in the near-IR region (λmax =818 nm) with a quantum yield of 2 % upon excitation at λ=482 nm. Its photoluminescence was quenched upon substitution with a Na(+) ion. DFT calculations confirmed the superatom characteristics of the title compound and the sodium-substituted derivatives.

  4. What Coexists with the Ferromagnetic Metallic Phase in Manganites?

    Energy Technology Data Exchange (ETDEWEB)

    Burkhardt, Mark H.; Hossain, M.A.; Sarkar, S.; Achkar, A.J.; Hawthorn, D.G.; Sutarto, R.; Chuang, 5 Y.-D.; Gonzalez, A.G.Cruz; Choi, Y.J.; Cheong, S.-W.; Durr, H.A.; Stohr, J.

    2012-07-25

    Colossal magnetoresistance, whereby the application of a magnetic field reduces the resistivity of a manganite by orders of magnitude, is generally believed to occur because of coexisting phases. Development of a complete theory to explain the phenomenon requires that the exact nature of these phases be known. We used resonant elastic soft x-ray scattering to examine the superlattice order that exists in La{sub 0.35}Pr{sub 0.275}Ca{sub 0.375}MnO{sub 3} above and below the Curie temperature. By measuring the resonance profile of the scattered x-rays at different values of q, we disentangle the contributions of orbital order and antiferromagnetism to the scattering signal above the Curie temperature. Below the Curie temperature, we see no signal from orbital order, and only antiferromagnetism coexists with the dominant ferromagnetic metallic phase.

  5. The role of the alkali and chalcogen atoms on the stability of the layered chalcogenide \\mathbf{{{A}_{2}}{{M}^{II}}M_{3}^{\\,IV}{{Q}_{8}}} (A  =  alkali-metal M  =  metal-cations Q  =  chalcogen) compounds: a density functional theory investigation within van der Waals corrections

    Science.gov (United States)

    Besse, Rafael; Da Silva, Juarez L. F.

    2017-01-01

    There is a great interest to design two-dimensional (2D) chalcogenide materials, however, our atomistic understanding of the major physical parameters that drive the formation of 2D or three-dimensional (3D) chalcogenides is far from satisfactory, in particular, for complex quaternary systems. To address this problem, we selected a set of quaternary 2D and 3D chalcogenide compounds, namely, {{\\text{A}}2}\\text{ZnS}{{\\text{n}}3}{{\\text{Q}}8} (A  =  Li, K, Cs; Q  =  S, Se, Te), which were investigated by density functional theory calculations within van der Waals (vdW) corrections. Employing experimental crystal structures and well designed crystal modifications, we found that the average atomic radius of the alkali-metal, A, and chalcogen, Q, species play a crucial role in the stability of the 2D structures. For example, the 2D structures are energetically favored for smaller (R1.8~{\\mathring{\\text{A}}}) average atomic radius, while 3D structures are favored at intermediate average atomic radius. Those results are explained in terms of strain minimization and Coulomb repulsion of the anionic species in the structure framework. Furthermore, the equilibrium lattice parameters are in excellent agreement with experimental results. Thus, the present insights can help in the design of stable quartenary 2D chalcogenide compounds.

  6. Liquid alkali metals - Equation of state and reduced-pressure, bulk-modulus, sound-velocity, and specific-heat functions

    Science.gov (United States)

    Schlosser, Herbert; Ferrante, John

    1989-01-01

    The previous work of Schlosser and Ferrante (1988) on universality in solids is extended to the study of liquid metals. As in the case of solids, to a good approximation, in the absence of phase transitions, plots of the logarithm of the reduced-pressure function H, of the reduced-isothermal-bulk-modulus function b, and of the reduced-sound-velocity function v are all linear in 1-X. Finally, it is demonstrated that ln(Cp/C/v) is also linear in 1-X, where X = (V/V/0/)exp 1/3), and V(0) is the volume at zero pressure.

  7. Topological Phase Transition in Metallic Single-Wall Carbon Nanotube

    Science.gov (United States)

    Okuyama, Rin; Izumida, Wataru; Eto, Mikio

    2017-01-01

    The topological phase transition is theoretically studied in a metallic single-wall carbon nanotube (SWNT) by applying a magnetic field B parallel to the tube. The Z topological invariant, winding number, is changed discontinuously when a small band gap is closed at a critical value of B, which can be observed as a change in the number of edge states owing to the bulk-edge correspondence. This is confirmed by numerical calculations for finite SWNTs of ˜1 µm length, using a one-dimensional lattice model to effectively describe the mixing between σ and π orbitals and spin-orbit interaction, which are relevant to the formation of the band gap in metallic SWNTs.

  8. NGNP Process Heat Utilization: Liquid Metal Phase Change Heat Exchanger

    Energy Technology Data Exchange (ETDEWEB)

    Piyush Sabharwall; Mike Patterson; Vivek Utgikar; Fred Gunnerson

    2008-09-01

    One key long-standing issue that must be overcome to fully realize the successful growth of nuclear power is to determine other benefits of nuclear energy apart from meeting the electricity demands. The Next Generation Nuclear Plant (NGNP) will most likely be producing electricity and heat for the production of hydrogen and/or oil retrieval from oil sands and oil shale to help in our national pursuit of energy independence. For nuclear process heat to be utilized, intermediate heat exchange is required to transfer heat from the NGNP to the hydrogen plant or oil recovery field in the most efficient way possible. Development of nuclear reactor - process heat technology has intensified the interest in liquid metals as heat transfer media because of their ideal transport properties. Liquid metal heat exchangers are not new in practical applications. An important rational for considering liquid metals is the potential convective heat transfer is among the highest known. Thus explains the interest in liquid metals as coolant for intermediate heat exchange from NGNP. For process heat it is desired that, intermediate heat exchangers (IHX) transfer heat from the NGNP in the most efficient way possible. The production of electric power at higher efficiency via the Brayton Cycle, and hydrogen production, requires both heat at higher temperatures and high effectiveness compact heat exchangers to transfer heat to either the power or process cycle. Compact heat exchangers maximize the heat transfer surface area per volume of heat exchanger; this has the benefit of reducing heat exchanger size and heat losses. High temperature IHX design requirements are governed in part by the allowable temperature drop between the outlet and inlet of the NGNP. In order to improve the characteristics of heat transfer, liquid metal phase change heat exchangers may be more effective and efficient. This paper explores the overall heat transfer characteristics and pressure drop of the phase change

  9. Control of phase boundary evolution in metal solidification for new thermodynamic parameters of the metal

    Science.gov (United States)

    Albu, A. F.

    2016-05-01

    The problem of controlling the phase boundary evolution in the course of solidification of metals with different thermodynamic properties is studied. The underlying mathematical model of the process is based on a three-dimensional nonstationary two-phase initial-boundary value problem of the Stefan type. The control functions are determined by optimal control problems, which are solved numerically with the help of gradient optimization methods. The gradient of the cost function is exactly computed by applying the fast automatic differentiation technique. The research results are described and analyzed. Some of them are illustrated.

  10. 氢原子能级与碱金属原子能级的比较研究%Comparative Studying of Hydrogen Atomic Energy Level and Alkali Metal Atomic Energy Level

    Institute of Scientific and Technical Information of China (English)

    王建伟; 蒲小芹

    2014-01-01

    The article by Bohr theory and The analysis of forces method, considered the interaction of different sit-uation, hydrogen atoms with alkali metal atomic energy level structure have been analyzed, and the numerical cal-culation, energy level diagram have been drawn out., Hydrogen energy and alkali metal atomic energy level were compared, by using the method of comparative study on the similarities and differences are found out.%运用玻尔理论及受力分析的方法,考虑相互作用的不同情况,分析了氢原子与碱金属原子能级结构,并进行了数值计算,画出了能级结构图。再运用比较研究的方法对氢原子能级与碱金属原子能级进行比较,找出其相同点及不同点。

  11. Mechanism of Effect of Copper and Alkali Metal on Properties of Varistor Ceramics%铜和碱金属影响压敏陶瓷性能的机理

    Institute of Scientific and Technical Information of China (English)

    曹全喜; 籍聪麟; 周晓华; 高锦秀

    2001-01-01

    从对ZnO和SrTiO3的晶体结构参数的计算出发,论述了铜和碱金属原子在这两种晶体中所处的位置。实验结果证实,同一种原子在不同的材料中可以起不同的作用。文章还讨论了这些杂质对压敏陶瓷的压敏电压、电容量、有效相对介电系数影响的机理。%According to the crystal structures of ZnO and SrTiO3,the positions of copper atoms and alkali metal atoms in the ceramic materials are discussed.It is shown as experiment result that the same atoms could have different roles in different crystal structures.The mechanism that copper atoms and alkali metal atoms have effects on breakdown voltage,capacitance and effective relative pemrmittivity of varistor ceramics are researched in the paper.

  12. A multinuclear solid-state NMR study of alkali metal ions in tetraphenylborate salts, M[BPh4] (M = Na, K, Rb and Cs): what is the NMR signature of cation-pi interactions?

    Science.gov (United States)

    Wu, Gang; Terskikh, Victor

    2008-10-16

    We report a multinuclear solid-state ( (23)Na, (39)K, (87)Rb, (133)Cs) NMR study of tetraphenylborate salts, M[BPh 4] (M = Na, K, Rb, Cs). These compounds are isostructural in the solid state with the alkali metal ion surrounded by four phenyl groups resulting in strong cation-pi interactions. From analyses of solid-state NMR spectra obtained under stationary and magic-angle spinning (MAS) conditions at 11.75 and 21.15 T, we have obtained the quadrupole coupling constants, C Q, and the chemical shift tensor parameters for the alkali metal ions in these compounds. We found that the observed quadrupole coupling constant for M (+) in M[BPh 4] is determined by a combination of nuclear quadrupole moment, Sternheimer antishielding factor, and unit cell dimensions. On the basis of a comparison between computed paramagnetic and diamagnetic contributions to the total chemical shielding values for commonly found cation-ligand interactions, we conclude that cation-pi interactions give rise to significantly lower paramagnetic shielding contributions than other cation-ligand interactions. As a result, highly negative chemical shifts are expected to be the NMR signature for cations interacting exclusively with pi systems.

  13. Large resistivity modulation in mixed-phase metallic systems

    Science.gov (United States)

    Lee, Yeonbae; Liu, Zhiqi; Heron, John; Clarkson, James; Hong, Jeongmin; Ko, Changhyun; Biegalski, Michael; Aschauer, Ulrich; Hsu, Shang-Lin; Nowakowski, Mark; Wu, Junqiao; Christen, Hans; Salahuddin, Sayeef; Bokor, Jeffrey; Spaldin, Nicola; Schlom, Darrell; Ramesh, Ramamoorthy

    2015-03-01

    We have investigated the effect of an electric field to FeRh/PMN-PT heterostructures and report 8% change in the electrical resistivity of FeRh films. Such a ``giant'' electroresistance (GER) response is striking in metallic systems, in which external electric fields are screened and thus only weakly influence the carrier concentrations and mobilities. We show that our FeRh films comprise coexisting ferromagnetic and antiferromagnetic phases with different resistivities, and the origin of the GER effect is the strain-mediated change in their relative proportions. The observed behavior is reminiscent of colossal magnetoresistance in perovskite manganites, and illustrates the role of mixed-phase coexistence in achieving large changes in physical properties with low-energy external perturbation.

  14. Phase separation of metallic hydrogen-helium alloys

    Science.gov (United States)

    Straus, D. M.; Ashcroft, N. W.; Beck, H.

    1977-01-01

    Calculations are presented for the thermodynamic functions and phase-separation boundaries of solid metallic hydrogen-helium alloys at temperatures between zero and 19,000 K and at pressures between 15 and 90 Mbar. Expressions for the band-structure energy of a randomly disordered alloy (including third order in the electron-ion interaction) are derived and evaluated. Short- and long-range orders are included by the quasi-chemical method, and lattice dynamics in the virtual-crystal harmonic approximation. It is concluded that at temperatures below 4000 K, there is essentially complete phase separation of hydrogen-helium alloys and that a miscibility gap remains at the highest temperatures and pressures considered. The relevance of these results to models of the deep interior of Jupiter is briefly discussed.

  15. Simultaneous Synthesis of Dimethyl Carbonate and Poly(ethylene terephthalate) Using Alkali Metals as Catalysts%碱金属化合物催化同时合成碳酸二甲酯和聚对苯二甲酸乙二醇酯

    Institute of Scientific and Technical Information of China (English)

    张丹; 王庆印; 姚洁; 王越; 曾毅; 王公应

    2007-01-01

    Dimethyl carbonate (DMC) and poly(ethylene terephthalate) was simultaneously synthesized by the transesterification of ethylene carbonate (EC) with dimethyl terephthalate (DMT) in this paper. This reaction is an excellent green chemical process without poisonous substance. Various alkali metals were used as the catalysts. The results showed alkali metals had catalytic activity in a certain extent. The effect of reaction condition was also studied. When the reaction was carried out under the following conditions: the reaction temperature 250℃, molar ratio of EC to DMT 3: 1, reaction time 3h, and catalyst amount 0.004 (molar ratio to DMT), the yield of DMC was 68.9%.

  16. First-principles study on saturated adsorption of alkali metal atoms on silicene%硅烯饱和吸附碱金属原子的第一性原理研究∗

    Institute of Scientific and Technical Information of China (English)

    黄艳平; 袁健美; 郭刚; 毛宇亮

    2015-01-01

    基于密度泛函理论的第一性原理计算,研究了硅烯饱和吸附碱金属元素原子的稳定性、微观几何结构和电子性质,并与纯硅烯及其饱和氢化结构进行了对比分析.研究发现复合物SiX (X =Li, Na, K, Rb)的形成能都是负的,相对于纯硅烯来说可以稳定存在. Bader电荷分析表明,电荷从碱金属原子转移至硅原子.从成键方式来看,硅烯与氢原子形成共价键,而与碱金属原子之间形成的键主要是离子性成键,但还存在部分共价关联成分.能带计算表明,锂原子饱和吸附在硅烯形成的复合物SiLi是直接带隙的半导体,带隙大小为0.34 eV.其他碱金属饱和吸附在硅烯上形成的复合物都表现为金属性.%Based on density functional first-principles calculations, we study the stability, micro-geometry, and electronic properties of alkali metal atoms adsorbed on silicene, and perform the comparison between pure and hydrogen-saturated silicenes. We found that all the formation energies of SiX (X = Li, Na, K and Rb) are negative, indicating that the relative structural stability of these new compounds is higher than silicene. Bader charge analysis shows that electric charge is transferred from Si atoms to H atoms in SiH compound, but in SiX the direction of charge transfer is opposite, i.e., the charge is transferred from alkali metal atoms to Si atoms. From the viewpoint of chemical bonding, it can be regarded that valence bond is formed between Si atoms and H atoms, and the bonds between Si and alkali metal atoms are mainly ionic, but there exists covalent contribution. From the band structure calculations, it is also found that the new type compound SiLi is a semiconductor with a direct band gap of 0.34 eV; however, all the other compounds of SiX(X =Na, K and Rb) exhibit metallic property.

  17. Distinguishing Isomeric Peptides: The Unimolecular Reactivity and Structures of (LeuPro)M(+) and (ProLeu)M(+) (M = Alkali Metal).

    Science.gov (United States)

    Jami-Alahmadi, Yasaman; Linford, Bryan D; Fridgen, Travis D

    2016-12-29

    The unimolecular chemistries and structures of gas-phase (ProLeu)M(+) and (LeuPro)M(+) complexes when M = Li, Na, Rb, and Cs have been explored using a combination of SORI-CID, IRMPD spectroscopy, and computational methods. CID of both (LeuPro)M(+) and (ProLeu)M(+) showed identical fragmentation pathways and could not be differentiated. Two of the fragmentation routes of both peptides produced ions at the same nominal mass as (Pro)M(+) and (Leu)M(+), respectively. For the litiated peptides, experiments revealed identical IRMPD spectra for each of the m/z 122 and 138 ions coming from both peptides. Comparison with computed IR spectra identified them as the (Pro)Li(+) and (Leu)Li(+), and it is concluded that both zwitterionic and canonical forms of (Pro)Li(+) exist in the ion population from CID of both (ProLeu)Li(+) and (LeuPro)Li(+). The two isomeric peptide complexes could be distinguished using IRMPD spectroscopy in both the fingerprint and the CH/NH/OH regions. The computed IR spectra for the lowest energy structures of each charge solvated complexes are consistent with the IRMPD spectra in both regions for all metal cation complexes. Through comparison between the experimental spectra, it was determined that in lithiated and sodiated ProLeu, metal cation is bound to both carbonyl oxygens and the amine nitrogen. In contrast, the larger metal cations are bound to the two carbonyls, while the amine nitrogen is hydrogen bonded to the amide hydrogen. In the lithiated and sodiated LeuPro complexes, the metal cation is bound to the amide carbonyl and the amine nitrogen while the amine nitrogen is hydrogen bonded to the carboxylic acid carbonyl. However, there is no hydrogen bond in the rubidiated and cesiated complexes; the metal cation is bound to both carbonyl oxygens and the amine nitrogen. Details of the position of the carboxylic acid C═O stretch were especially informative in the spectroscopic confirmation of the lowest energy computed structures.

  18. Selection of non-adsorbing alkali components

    Energy Technology Data Exchange (ETDEWEB)

    Lee, S.H.D.; Natesan, K.; Swift, W.M.

    1992-11-01

    This project consists of three phases of laboratory experimental study. In phase I (screening), eight candidate materials, 304SS (serves as a base material for comparison), Hastelloy C-276, Hastelloy X, Haynes No. 188, Allonized 304SS, Pt-coated 304SS, and ceramic-coated 304SS, will be subjected to atmospheric TGA study under the simulated PFBC (oxidizing) environment with and without alkali vapor doping. Each candidate material will be evaluated for its resistance toward alkali-vapor capture. In addition, a post-test metallographic characterization of the sample will be performed to obtain a better understanding of the alkali capture mechanism and material behavior. The material(s) with little or no alkali-vapor adsorption will be selected as the promising material(s) for the Phase II study. In Phase II, the promising material(s) will be further tested in the TGA under elevated pressure to simulate the PFBC environment (in terms of temperature, pressure, and gas composition). The effect of pressure on the extent of alkali-vapor adsorption will be evaluated, and the test samples will be metallographically characterized. The most promising candidate material(s) will be identified and recommended for further tesfing in the actual PFBC environment. In Phase III, four materials will be selected from the eight candidate materials screened in the PFBC environment and will be evaluated for their alkali-vapor capture by atmospheric TGA under the coal gasification fuel gas (reducing) environment. The tested samples will also be metallographically characterized. The most promising material(s) will be identified and recommended for further testing in the actual coal gasification environment.

  19. Selection of non-adsorbing alkali components

    Energy Technology Data Exchange (ETDEWEB)

    Lee, S.H.D.; Natesan, K.; Swift, W.M.

    1992-01-01

    This project consists of three phases of laboratory experimental study. In phase I (screening), eight candidate materials, 304SS (serves as a base material for comparison), Hastelloy C-276, Hastelloy X, Haynes No. 188, Allonized 304SS, Pt-coated 304SS, and ceramic-coated 304SS, will be subjected to atmospheric TGA study under the simulated PFBC (oxidizing) environment with and without alkali vapor doping. Each candidate material will be evaluated for its resistance toward alkali-vapor capture. In addition, a post-test metallographic characterization of the sample will be performed to obtain a better understanding of the alkali capture mechanism and material behavior. The material(s) with little or no alkali-vapor adsorption will be selected as the promising material(s) for the Phase II study. In Phase II, the promising material(s) will be further tested in the TGA under elevated pressure to simulate the PFBC environment (in terms of temperature, pressure, and gas composition). The effect of pressure on the extent of alkali-vapor adsorption will be evaluated, and the test samples will be metallographically characterized. The most promising candidate material(s) will be identified and recommended for further tesfing in the actual PFBC environment. In Phase III, four materials will be selected from the eight candidate materials screened in the PFBC environment and will be evaluated for their alkali-vapor capture by atmospheric TGA under the coal gasification fuel gas (reducing) environment. The tested samples will also be metallographically characterized. The most promising material(s) will be identified and recommended for further testing in the actual coal gasification environment.

  20. Facilitated alkali ion transfer at the water 1,2-dichloroethane interphase Ab-initio calculations concerning alkaline metal cation - 1,10-phenanthroline complexes

    CERN Document Server

    Sánchez, C; Baruzzi, A M; Leiva, E P M

    1997-01-01

    A series of calculations on the energetics of complexation of alkaline metals with 1,10-phenanthroline are presented. It is an experimental fact that the ordering of the free energy of transfer across the water - 1,2-dichloroethane interphase is governed by the charge / size ratio of the diferent cations; the larger cations showing the lower free energy of transfer. This ordering of the free energies of transfer is reverted in the presence of 1,10-phenanthroline in the organic phase. We have devised a thermodynamic cycle for the transfer process and by means of ab-initio calculations have drawn the conclusion that in the presence of phen the free energy of transfer is governed by the stability of the PHEN/M $^{+}$complex, which explains the observed tendency from a theoretical point of view.

  1. Thermodynamic considerations of the vapor phase reactions in III–nitride metal organic vapor phase epitaxy

    Science.gov (United States)

    Sekiguchi, Kazuki; Shirakawa, Hiroki; Chokawa, Kenta; Araidai, Masaaki; Kangawa, Yoshihiro; Kakimoto, Koichi; Shiraishi, Kenji

    2017-04-01

    We analyzed the metal organic vapor phase epitaxial growth mechanism of the III–nitride semiconductors GaN, AlN, and InN by first-principles calculations and thermodynamic analyses. In these analyses, we investigated the decomposition processes of the group III source gases X(CH3)3 (X = Ga, Al, In) at finite temperatures and determined whether the (CH3)2GaNH2 adduct can be formed or not. The results of our calculations show that the (CH3)2GaNH2 adduct cannot be formed in the gas phase in GaN metal organic vapor phase epitaxy (MOVPE), whereas, in AlN MOVPE, the formation of the (CH3)2AlNH2 adduct in the gas phase is exclusive. In the case of GaN MOVPE, trimethylgallium (TMG, [Ga(CH3)3]) decomposition into Ga gas on the growth surface with the assistance of H2 carrier gas, instead of the formation of the (CH3)2GaNH2 adduct, occurs almost exclusively. Moreover, in the case of InN MOVPE, the formation of the (CH3)2InNH2 adduct does not occur and it is relatively easy to produce In gas even without H2 in the carrier gas.

  2. 双层石墨烯吸附碱金属原子的第一性原理研究%First-principles study of alkali metal adsorptions on bilayer graphene

    Institute of Scientific and Technical Information of China (English)

    杨绍斌; 李思南; 唐树伟; 沈丁; 孙闻; 董伟

    2016-01-01

    基于密度泛函的第一性原理方法,研究了Li、Na、K和Rb碱金属原子吸附在双层石墨烯( BLG)表面的吸附能、迁移行为、电子性能。研究发现,Li和Na原子在BLG表面吸附易形成团簇,K和Rb原子能够分散吸附。碱金属原子在BLG表面的扩散能垒随原子半径的增加而减小。碱金属原子吸附使电子部分转移至BLG,使体系Fermi能级贯穿导带,表现出金属性。电荷密度差和电荷转移的分析表明,Li、Na、K和Rb与BLG表面以离子键结合。%Using the first-principles method based on the density functional theory, the adsorption energies, migration processes and electronic properties for the Li, Na, K and Rb adsorbed on the bilayer graphene ( BLG) were calculated. The calculated adsorption energies indicate that both Li and Na atoms tend to aggregate into clusters, and the K and Rb atoms can dispersive on the BLG. The energy barriers for alkali-metal atoms migra-tion decrease with the increasing of the atomic radius. The adsorption systems exhibit metallic character since the Fermi level shifts up into the conduction band due to the electrons transfer from adatoms to the BLG. Analysis of the charge density differences and electronic structures of these adsorption systems shows that ionic bond takes place between the alkali-metal atoms ( Li, Na, K and Rb) and the BLG.

  3. Impact of Nanograting Phase-Shift on Light Absorption Enhancement in Plasmonics-Based Metal-Semiconductor-Metal Photodetectors

    Directory of Open Access Journals (Sweden)

    Narottam Das

    2011-01-01

    Full Text Available The finite difference time-domain (FDTD method is used to simulate the light absorption enhancement in a plasmonic metal-semiconductor-metal photodetector (MSM-PD structure employing a metal nanograting with phase shifts. The metal fingers of the MSM-PDs are etched at appropriate depths to maximize light absorption through plasmonic effects into a subwavelength aperture. We also analyse the nano-grating phase shift and groove profiles obtained typically in our experiments using focused ion beam milling and atomic force microscopy and discuss the dependency of light absorption enhancement on the nano-gratings phase shift and groove profiles inscribed into MSM-PDs. Our simulation results show that the nano-grating phase shift blue-shifts the wavelength at which the light absorption enhancement is maximum, and that the combined effects of the nano-grating groove shape and phase shift degrade the light absorption enhancement by up to 50%.

  4. Thermodynamic Functions and Phase Transformation of Metal Nanocrystals

    Institute of Scientific and Technical Information of China (English)

    Jinping GAO; Xiaoyan SONG; Jiuxing ZHANG; Keyong YANG; Xuemei LIU

    2005-01-01

    A model to calculate the thermodynamic functions of the pure metal nanocrystals has been developed, with the consideration of the effects of both the interfaces and the crystal in the nano-grain interior. As an example, the enthalpy, entropy and Gibbs free energy, as functions of the excess free volume at interfaces, temperature and grain size, are calculated for the Co nanocrystals. Furthermore, the characteristics ofβ-Co→α-Co phase transformation are studied, and the transformation temperatures at different levels of grain size, as well as the critical grain sizes at different temperatures, are predicted. The calculation results show that, the nano-grainedβ-Co (fcc) is thermodynamically stable at temperatures much lower than that for the conventional coarse-grained materials, and may also stably exist at room temperature when the grain size is reduced to be small enough. The present model is verified by comparisons between the experimental findings and the theoretical predictions.

  5. Microfabrication of MEMS alkali metal vapor cells for chip-scale atomic devices%芯片级原子器件MEMS碱金属蒸气腔室制作

    Institute of Scientific and Technical Information of China (English)

    尤政; 马波; 阮勇; 陈硕; 张高飞

    2013-01-01

    提出了基于两步低温阳极键合工艺的碱金属蒸气腔室制作方法,用于实现原子钟、原子磁力计及原子陀螺仪等器件的芯片级集成.由微机电系统(MEMS)体硅工艺制备了腔室结构.首先采用标准工艺将刻蚀有腔室的硅圆片与Pyrex玻璃阳极键合成预成型腔室,然后引入氮缓冲气体和由惰性石蜡包覆的微量碱金属铷或铯.通过两步阳极键合来密封腔室,键合温度低于石蜡燃点198℃.第一步键合预封装腔室,键合电压小于缓冲气体的击穿电压.第二步键合在大气氛围中进行,电压增至1 200 V来增强封装质量.通过高功率激光器局部加热释放碱金属,同时在腔壁上形成均匀的石蜡镀层以延长极化原子寿命.本文实现了160℃的低温阳极键合封装,键合率达到95%以上.封装的碱金属铷释放后仍具有金属光泽,实现的最小双腔室体积为6.5 mm×4.5 mm×2 mm.铷的吸收光谱表明铷有效地封装在腔室中,证明两步低温阳极键合工艺制作碱金属蒸气腔室是可行的.%This paper reported on the microfabrication of alkali metal vapor cells based on the two-step low temperature anodic bonding for the chip-scale integration of atomic clock,atomic magnetometer,atomic gyroscope and other atomic devices.Cell structures were fabricated by Micro-electromechanical System (MEMS) bulk silicon process,and the etched silicon with cells was firstly bonded to Pyrex glass to fabricate preformed chambers by the standard anodic bonding process.Then,nitrogen buffer gas and micro-scale alkali metal (rubidium or cesium) were introduced into the preformed cells.The two-step anodic bonding process was used to seal the cells at a temperature lower than the paraffin flash point (198 ℃).In the first step,bonding voltage was lower than the breakdown voltage of nitrogen buffer gas to pre-seal the cells.In the second step,the bonding was in air atmosphere,and the bonding voltage increased up to 1

  6. Comparative study of reversible hydrogen storage in alkali-doped fulleranes

    Energy Technology Data Exchange (ETDEWEB)

    Teprovich, Joseph A.; Knight, Douglas A.; Peters, Brent [Clean Energy Directorate – Savannah River National Laboratory, Aiken, SC 29801 (United States); Zidan, Ragaiy, E-mail: ragaiy.zidan@srnl.doe.gov [Clean Energy Directorate – Savannah River National Laboratory, Aiken, SC 29801 (United States)

    2013-12-15

    Highlights: ► Catalytic effect of alkali metals of fullerane formation. ► Hydrogen storage properties of alkali metal hydrides and fullerene composites. ► Novel intercalation of Na and Li in the fullerene lattice. ► Reversible phase transformation of C{sub 60} from fcc to bcc upon de/rehydrogenation. ► Potential to enable to the formation of other carbon based hydrogen storage systems. -- Abstract: In this report we describe and compare the hydrogen storage properties of lithium and sodium doped fullerenes prepared via a solvent-assisted mixing process. For the preparation of these samples either NaH or LiH was utilized as the alkali metal source to make material based on either a Na{sub 6}C{sub 60} or Li{sub 6}C{sub 60}. Both of the alkali-doped materials can reversibly absorb and desorb hydrogen at much milder conditions than the starting materials used to make them (decomposition temperatures of NaH > 420 °C, LiH > 670 °C, and fullerane > 500 °C). The hydrogen storage properties of the materials were compared by TGA, isothermal desorption, and XRD analysis. It was determined that the sodium-doped material can reversibly store 4.0 wt.% H{sub 2} while the lithium doped material can reversibly store 5.0 wt.% H{sub 2} through a chemisorption mechanism indicated by the formation and measurement of C–H bonds. XRD analysis of the material demonstrated that a reversible phase transition between fcc and bcc occurs depending on the temperature at which the hydrogenation is performed. In either system the active hydrogen storage material resembles a hydrogenated fullerene (fullerane)

  7. Ab initio study of the adsorption, diffusion, and intercalation of alkali metal atoms on the (0001) surface of the topological insulator Bi{sub 2}Se{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Ryabishchenkova, A. G., E-mail: ryaange@gmail.com; Otrokov, M. M.; Kuznetsov, V. M.; Chulkov, E. V. [Tomsk State University (Russian Federation)

    2015-09-15

    Ab initio study of the adsorption, diffusion, and intercalation of alkali metal adatoms on the (0001) step surface of the topological insulator Bi{sub 2}Se{sub 3} has been performed for the case of low coverage. The calculations of the activation energies of diffusion of adatoms on the surface and in van der Waals gaps near steps, as well as the estimate of diffusion lengths, have shown that efficient intercalation through steps is possible only for Li and Na. Data obtained for K, Rb, and Cs atoms indicate that their thermal desorption at high temperatures can occur before intercalation. The results have been discussed in the context of existing experimental data.

  8. New methods and materials for solid phase extraction and high performance liquid chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Dumont, Philip John [Iowa State Univ., Ames, IA (United States)

    1996-04-23

    This paper describes methods for solid phase extraction and high performance liquid chromatography (HPLC). The following are described: Effects of Resin Sulfonation on the Retention of Polar Organic Compounds in Solid Phase Extraction; Ion-Chromatographic Separation of Alkali Metals In Non-Aqueous Solvents; Cation-Exchange Chromatography in Non-Aqueous Solvents; and Silicalite As a Stationary Phase For HPLC.

  9. Promoting oxygen vacancy formation and p-type conductivity in SrTiO3via alkali metal doping: a first principles study.

    Science.gov (United States)

    Triggiani, Leonardo; Muñoz-García, Ana B; Agostiano, Angela; Pavone, Michele

    2016-10-19

    Strontium titanate (SrTiO3, STO) is a prototypical perovskite oxide, widely exploited in many technological applications, from catalysis to energy conversion devices. In the context of solid-oxide fuel cells, STO has been recently applied as an epitaxial substrate for nano-sized layers of mixed ion-electron conductive catalysts with enhanced electrochemical performances. To extend the applications of such heterogeneous nano-cathodes in real devices, also the STO support should be active for both electron transport and oxide diffusion. To this end, we explored using first-principles calculations the strategy of doping of STO at the Sr site with sodium and potassium. These two ions fit in the perovskite structure and induce holes in the STO valence band, so as to obtain the desired p-type electronic conduction. At the same time, the doping with alkali ions also promotes the formation of oxygen vacancies in STO, a prerequisite for effective oxide diffusion. Analysis of electron density rearrangements upon defect formation allows relating the favorable vacancy formation energies to an improved electronic delocalization over the oxide sub-lattice, as observed in closely related materials (e.g. Sr2Fe1.5Mo0.5O6). Overall, our results suggest the alkali-doped STO as a new potential substrate material in nanoscale heterogeneous electrodes for solid oxide electrochemical cells.

  10. Critical points of metal vapors

    Energy Technology Data Exchange (ETDEWEB)

    Khomkin, A. L., E-mail: alhomkin@mail.ru; Shumikhin, A. S. [Russian Academy of Sciences, Joint Institute for High Temperatures (Russian Federation)

    2015-09-15

    A new method is proposed for calculating the parameters of critical points and binodals for the vapor–liquid (insulator–metal) phase transition in vapors of metals with multielectron valence shells. The method is based on a model developed earlier for the vapors of alkali metals, atomic hydrogen, and exciton gas, proceeding from the assumption that the cohesion determining the basic characteristics of metals under normal conditions is also responsible for their properties in the vicinity of the critical point. It is proposed to calculate the cohesion of multielectron atoms using well-known scaling relations for the binding energy, which are constructed for most metals in the periodic table by processing the results of many numerical calculations. The adopted model allows the parameters of critical points and binodals for the vapor–liquid phase transition in metal vapors to be calculated using published data on the properties of metals under normal conditions. The parameters of critical points have been calculated for a large number of metals and show satisfactory agreement with experimental data for alkali metals and with available estimates for all other metals. Binodals of metals have been calculated for the first time.

  11. Influence of the alkali metal cation on the fragmentation of monensin in ESI-MS/MS Influência de cátions de metais alcalinos sobre a fragmentação de monensina em ESI-MS/MS

    Directory of Open Access Journals (Sweden)

    Norberto Peporine Lopes

    2006-09-01

    Full Text Available The MS/MS fragmentation of the alkali metal complexes of monensin A are studied. The increase in alkali metal ionic radii decreases the ability of the Grob-Wharton fragmentation mechanism to occur and reduces the overall degree of fragmentation. Conversely, the electronegativity of the metal cation is related to the number of fragment ions observed.O presente trabalho relata os estudos de fragmentação por espectrometria de massas seqüencial de complexos formados pela monensina A e uma série de metais alcalinos. Foi observado que o aumento do raio iônico do metal alcalino levou a uma diminuição do mecanismo de fragmentação do tipo Grob-Wharton e ao grau de fragmentação. Por outro lado, a maior eletronegatividade mostrou estar relacionada ao número de fragmentos observados.

  12. Reaction phases and diffusion paths in SiC/metal systems

    Energy Technology Data Exchange (ETDEWEB)

    Naka, M.; Fukai, T. [Osaka Univ., Osaka (Japan); Schuster, J.C. [Vienna Univ., Vienna (Austria)

    2004-07-01

    The interface structures between SiC and metal are reviewed at SiC/metal systems. Metal groups are divided to carbide forming metals and non-carbide forming metals. Carbide forming metals form metal carbide granular or zone at metal side, and metal silicide zone at SiC side. The further diffusion of Si and C from SiC causes the formation of T ternary phase depending metal. Non-carbide forming metals form silicide zone containing graphite or the layered structure of metal silicide and metal silicide containing graphite. The diffusion path between SiC and metal are formed along tie-lines connecting SiC and metal on the corresponding ternary Si-C-M system. The reactivity of metals is dominated by the forming ability of carbide or silicide. Te reactivity tendency of elements are discussed on the periodical table of elements, and Ti among elements shows the highest reactivity among carbide forming metals. For non-carbide forming metals the reactivity sequence of metals is Fe>Ni>Co. (orig.)

  13. Study on migration behavior of alkali metals during co-gasification of corn stalk and PE%玉米秸秆与塑料PE共气化过程中碱金属迁移行为的研究

    Institute of Scientific and Technical Information of China (English)

    杨天华; 肖蕾; 开兴平; 丁一; 陈志敏; 李润东

    2013-01-01

    The migration behavior of alkali metals during co-gasification of cornstalk and PE in a fixed bed at different temperatures was studied on the thermodynamic equilibrium calculation,the X-ray power diffraction and scanning electron microscope/energy dispersive spectrometer.The results indicat that the alkali chlorides (KCl、K2Cl2 、NaCl)are the main components in gaseous.There is a large amounts of C and H in the fules with the mixed of plastic PE.The H makes the C1 prefer HC1 to KC1,meanwhile,the release radio of K is lower than the cornstalk gasification cause of the C easily reacted with K than Na.Alkali metal compounds in ashes are mainly in the forms of KCl,NaCl,K2SO4,KAlSi3O8,KAlSiO4,NaAlSi3O8,NaAlSiO4.The KCl,NaC1 begin to release when the reacting temperature above 800 ℃ and most of K,Na,Cl are easily deposited on the edge of the hole.%选取一定混合比例的玉米秸秆与塑料PE制成混合燃料,采用固定床实验台,通过改变反应温度,并结合化学热力学平衡分析、X射线衍射及扫描电子显微电镜能谱分析技术对共气化过程中碱金属的迁移行为进行研究.结果表明,气化气中碱金属以气态组元KCl、K2Cl2、NaCl形式存在.混合燃料中掺入塑料PE后,C、H含量增加,H使得共气化反应中更容易与Cl反应生成HCl,而非KCl,同时C更容易与K结合,导致K的释放率低于单独玉米秸秆气化,但使Na释放率增加.灰中碱金属化合物以KCl、NaCl、K2SO4、KAlSi3O8、KAlSiO4、NaAlSi3O8、NaAlSiO4为主,气化温度高于800℃后灰中K、Na、Cl更易沉积于微孔边缘.

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

    Science.gov (United States)

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

    2015-09-18

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

  15. Rydberg Matter clusters of alkali metal atoms: the link between meteoritic matter, polar mesosphere summer echoes (PMSE), sporadic sodium layers, polar mesospheric clouds (PMCs, NLCs), and ion chemistry

    CERN Document Server

    Olofson, Frans; Holmlid, Leif

    2010-01-01

    A material exists which links together the influx of meteoritic matter from interplanetary space, the polar mesosphere summer echoes (PMSE), the sporadic sodium layers, the polar mesospheric clouds (PMCs, NLCs), and the observed ion chemistry in the mesosphere. The evidence in these research fields is here analyzed and found to agree well with the properties of Rydberg Matter (RM). This material has been studied with numerous methods in the laboratory. Alkali atoms, mainly Na, reach the mesosphere in the form of interplanetary (meteoritic, cometary) dust. The planar RM clusters NaN usually contain N = 19, 37 or 61 atoms, and have the density of air at 90 km altitude where they float. The diameters of the clusters are 10-100 nm from laboratory high precision radio frequency spectroscopic studies. Such experiments show that RM clusters interact strongly with radar frequencies: this explains the radio frequency heating and reflection studies of PMSE layers. The clusters give the low temperature in the mesosphere...

  16. Matrix-assisted laser desorption mass spectrometry of gas-phase peptide-metal complexes

    Science.gov (United States)

    Hortal, Ana R.; Hurtado, Paola; Martínez-Haya, Bruno

    2008-12-01

    Cation attachment to a model peptide has been investigated in matrix-assisted laser desorption experiments. Angiotensin I (Asp-Arg-Val-Tyr-Ile-His-Pro-Phe-His-Leu) is chosen as a system for study, and Cu2+ and K+ salts are used as cationizing agents. Three fundamentally different types of samples are investigated: (1) a crystalline sample of Ang I, metal salt and MALDI matrix, prepared with the conventional dried droplet method; (2) a solvent-free fine powder mixture of the same three compounds, and (3) a solution of the angiotensin and the metal salt in an ionic liquid matrix (a molten organic salt that acts as a MALDI active solvent). Effective protonation and cationization of the peptide are achieved with the three methods. The transition metal systematically provides more efficient cationization than the alkali metal. At sufficiently high concentration of the salt, the attachment of up to four copper cations to the angiotensin is observed in the MALDI spectrum. In contrast, only one K+ cation is efficiently bound to the peptide. For a given salt concentration, the highest degree of cationization is obtained in the laser desorption from the ionic liquid matrix. This is attributed to the efficient transfer of free metal cations to the desorption plume, where the complexation takes place.

  17. Alkali promotion of N-2 dissociation over Ru(0001)

    DEFF Research Database (Denmark)

    Mortensen, Jens Jørgen; Hammer, Bjørk; Nørskov, Jens Kehlet

    1998-01-01

    Using self-consistent density functional calculations, we show that adsorbed Na and Cs lower the barrier for dissociation of N2 on Ru(0001). Since N2 dissociation is a crucial step in the ammonia synthesis reaction, we explain in this way the experimental observation that alkali metals promote...... the ammonia synthesis reaction over Ru catalysts. We also show that the origin of this effect is predominantly a direct electrostatic attraction between the adsorbed alkali atoms and the dissociating molecule....

  18. Fabrication of La2Ti2O7 crystals using an alkali-metal molybdate flux growth method and their nitridability to form LaTiO2N crystals under a high-temperature NH3 atmosphere.

    Science.gov (United States)

    Hojamberdiev, Mirabbos; Yamaguchi, Akiko; Yubuta, Kunio; Oishi, Shuji; Teshima, Katsuya

    2015-04-06

    Flux growth is a promising method that allows one to control over the crystalline phase, crystal shape, crystal size, and crystal surface through the selection of a suitable flux. In this work, lanthanum titanate (La2Ti2O7) crystals with different morphologies were grown using the Na2MoO4, K2MoO4, NaCl, and mixed NaCl + K2MoO4 (molar ratio = 3:7) fluxes, and their nitridability to form LaTiO2N crystals under a high-temperature NH3 atmosphere was also investigated. The effects of the solute concentration and cooling rate on the growth of the La2Ti2O7 crystals were also studied. The X-ray diffraction results revealed that the {100} plane was dominant in the La2Ti2O7 platelet crystals grown using the alkali-metal molybdate fluxes. When the solute concentration was increased from 1 to 20 mol %, the average size of the crystals decreased without considerable alteration of the overall crystal morphology. The La2Ti2O7 crystals with the preferred ⟨010⟩ and ⟨001⟩ growth directions along the b and c axes were grown using the Na2MoO4 and K2MoO4 fluxes, respectively. Compared to the Na2MoO4 flux, the K2MoO4 flux did not show a cooling-rate-dependent effect on the growth of the La2Ti2O7 crystals. It was found that conversion of the La2Ti2O7 crystals to the LaTiO2N crystals was strongly dependent on the flux used to grow the precursor La2Ti2O7 crystals. That is, the La2Ti2O7 crystals grown using the K2MoO4 and NaCl fluxes were nearly completely converted into the LaTiO2N crystals, while conversion of the La2Ti2O7 crystals grown using the Na2MoO4 and mixed NaCl + K2MoO4 fluxes to the LaTiO2N crystals seemed to be not completed yet even after nitridation at 950 °C for 15 h using NH3 because of the larger crystal size and the presence of unintentional impurities (sodium and molybdenum from the flux) in the La2Ti2O7 crystal lattice. Nevertheless, the LaTiO2N crystals fabricated by nitriding the La2Ti2O7 crystals grown using the K2MoO4 and NaCl fluxes should be suitable for

  19. Electrolytic systems and methods for making metal halides and refining metals

    Energy Technology Data Exchange (ETDEWEB)

    Holland, Justin M.; Cecala, David M.

    2015-05-26

    Disclosed are electrochemical cells and methods for producing a halide of a non-alkali metal and for electrorefining the halide. The systems typically involve an electrochemical cell having a cathode structure configured for dissolving a hydrogen halide that forms the halide into a molten salt of the halogen and an alkali metal. Typically a direct current voltage is applied across the cathode and an anode that is fabricated with the non-alkali metal such that the halide of the non-alkali metal is formed adjacent the anode. Electrorefining cells and methods involve applying a direct current voltage across the anode where the halide of the non-alkali metal is formed and the cathode where the non-alkali metal is electro-deposited. In a representative embodiment the halogen is chlorine, the alkali metal is lithium and the non-alkali metal is uranium.

  20. Metal-insulator phase transition in a VO2 thin film observed with terahertz spectroscopy

    DEFF Research Database (Denmark)

    Jepsen, Peter Uhd; Fischer, Bernd M.; Thoman, Andreas

    2006-01-01

    We investigate the dielectric properties of a thin VO2 film in the terahertz frequency range in the vicinity of the semiconductor-metal phase transition. Phase-sensitive broadband spectroscopy in the frequency region below the phonon bands of VO2 gives insight into the conductive properties...... of the film during the phase transition. We compare our experimental data with models proposed for the evolution of the phase transition. The experimental data show that the phase transition occurs via the gradual growth of metallic domains in the film, and that the dielectric properties of the film...

  1. Semiconductor-metal and semiconductor-magnetic half-metal phase transitions in layered SrAgSeF phases doped with oxygen and nitrogen

    Science.gov (United States)

    Bannikov, V. V.; Ivanovskii, A. L.

    2012-11-01

    Results of ab initio band calculations for a layered nonmagnetic SrAgSeF semiconductors consisting of [SrF]/[AgSe] alternating blocks show that the partial O → F substitution leads to a semiconductormetal phase transition due to "metallization" of the [AgSe] bocks. The oxygen-doped SrAgSeF1 - x O x phase possesses a metal/semiconductor periodic structure formed by alternating [AgSe] and [SrF1 - x O x ] blocks, respectively. On the contrary, the partial N → F substitution induces a semiconductor-magnetic half-metal phase transition. The resulting SrAgSeF1 - x N x system may be of interest as a new material for spintronics.

  2. Local structure of alkalis in mixed-alkali borate glass to elucidate the origin of mixed-alkali effect

    Directory of Open Access Journals (Sweden)

    Yomei Tokuda

    2015-12-01

    Full Text Available We report the structural analysis of Na+ and Cs+ in sodium cesium borate crystals and glasses using 23Na and 133Cs magic-angle spinning nuclear magnetic resonance (MAS NMR spectroscopy. The composition dependence of NMR spectra of the borate was similar to that of the silicate: (1 the peak position of cesium borate crystals shifted to upfield for structures with larger Cs+ coordination numbers, (2 the MAS NMR spectra of xNa2O-yCs2O-3B2O3 (x = 0, 0.25, 0.5, 0.75, 1.0, x + y = 1 glass showed that the average coordination number (CN of both the alkali cations decreases with increasing Cs+/(Na+ + Cs+ ratio. However, the degree of decrement in borates is much smaller than that in silicates. We have considered that the small difference in CN is due to 4-coordinated B, because it is electrically compensated by the alkali metal ions resulting in the restriction of having various coordinations of O to alkali metal.

  3. Stabilisation of late transition metal and noble metal films in hexagonal and body centred tetragonal phases by epitaxial growth

    Energy Technology Data Exchange (ETDEWEB)

    Hueger, E.

    2005-08-26

    In this work ultrathin metallic films with a crystal phase different to their natural bulk structure were produced by hetero-epitaxial growth on metallic substrates. A further aim of this work was to understand the initiation, growth and stability of crystal phase modifications of these films. there exist cases where the films turn beyond the pseudomorphic-growth to a crystal phase different from their natural bulk structure. The present work presents and discusses such a case in addition to the general phenomenon of pseudomorphic-growth. In particular it is shown that metals whose natural phase is face centred cubic (fcc) can be grown in body centred tetragonal (bct) or hexagonal close packed (hcp) phases in the form of thin films on (001) surfaces of appropriate substrates. The growth behavior, electron diffraction analysis, appearance conditions, geometric fit considerations, examples and a discussion of the phase stability of non-covered films and superlattices is given reviewing all epitaxial-systems whose diffraction pattern can be explained by the hexagonal or pseudomorphic bct phase. (orig.)

  4. Ecotoxicology of heavy metals: Liquid-phase extraction by nanosorbents

    Science.gov (United States)

    Burakov, A.; Romantsova, I.; Babkin, A.; Neskoromnaya, E.; Kucherova, A.; Kashevich, Z.

    2015-11-01

    The paper considers the problem of extreme toxicity heavy metal compounds dissolved in wastewater and liquid emissions of industrial enterprises to living organisms and environment as a whole. The possibility of increasing extraction efficiency of heavy metal ions by sorption materials was demonstrated. The porous space of the latter was modified by carbon nanotubes (CNTs) during process of the chemical vapour deposition (CVD) of carbon on metal oxide catalysts. The increasing of the sorption capacity (10-30%) and the sorption rate of nanomodified activated carbons in comparison with standard materials in the example of absorption of Co2+ and Ni2+ ions from aqueous solutions was proven.

  5. Calculation of Radiative Corrections to E1 matrix elements in the Neutral Alkalis

    Energy Technology Data Exchange (ETDEWEB)

    Sapirstein, J; Cheng, K T

    2004-09-28

    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 alkalis but significantly larger for the heavier alkalis, 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. Absorption spectra of alkali-C₆₀ nanoclusters.

    Science.gov (United States)

    Rabilloud, Franck

    2014-10-28

    We investigate the absorption spectra of alkali-doped C60 nanoclusters, namely C60Nan, C60Kn, and C60Lin, with n = 1, 2, 6, 12, in the framework of the time-dependent density-functional theory (TDDFT). We study the dependence of the absorption spectra on the nature of the alkali. We show that in few cases the absorption spectra depend on the arrangement of the alkali atoms over the fullerene, though sometimes the absorption spectra do not allow us to distinguish between different configurations. When only one or two alkali atoms are adsorbed on the fullerene, the optical response of alkali-doped C60 is similar to that of the anion C60(-) with a strong response in the UV domain. In contrast, for higher concentration of alkali, a strong optical response is predicted in the visible range, particularly when metal-metal bonds are formed. The weak optical response of the I(h)-symmetry C60Li12 is proposed to be used as a signature of its structure.

  7. PHASE CONVERSIONS IN METAL-OXIDE COMPOSITIONS ON THE BASIS OF ALUMINIUM AND SILICON OXIDE

    OpenAIRE

    2010-01-01

    The regularities of phase conversions in metal-oxide compositions on the basis of aluminium and silicon oxide with the purpose of silumins synthesis by means of direct restoration of aluminium silicon are studied.

  8. Comparing the sugar profiles and primary structures of alkali-extracted water-soluble polysaccharides in cell wall between the yeast and mycelial phases from Tremella fuciformis.

    Science.gov (United States)

    Zhu, Hanyu; Yuan, Yuan; Liu, Juan; Zheng, Liesheng; Chen, Liguo; Ma, Aimin

    2016-05-01

    To gain insights into dimorphism, cell wall polysaccharides from Tremella fuciformis strains were obtained from alkali-extracted water-soluble fractions PTF-M38 (from the mycelial form), PTF-Y3 and PTF-Y8 (from the yeast form) of T. fuciformis strains were used to gain some insights into dimorphism study. Their chemical properties and structural features were investigated using gel permeation chromatography, gas chromatography, UV and IR spectrophotometry and Congo red binding reactions. The results indicated that the backbones of PTF-M38, PTF-Y3 and PTF-Y8 were configured with α-linkages with average molecular weights of 1.24, 1.08, and 1.19 kDa, respectively. PTF-M38 was mainly composed of xylose, mannose, glucose, and galactose in a ratio of 1:1.47:0.48:0.34, while PTF-Y3 and PTF-Y8 were mainly composed of xylose, mannose and glucose in a ratio of 1:1.65:4.06 and 1:1.21:0.44, respectively. The sugar profiles of PTF-M38, PTF-Y3 and PTF-Y8 were also established for further comparison. These profiles showed that all three polysaccharides contained the same sugars but in different ratios, and the carbon sources (xylose, mannose, glucose, and galactose) affected the sugar ratios within the polysaccharides.

  9. Aqueous-phase hydrogenation of acetic acid over transition metal catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Olcay, Hakan [University of Massachusetts, Amherst; Xu, Lijun [ORNL; Xu, Ye [ORNL; Huber, George [University of Massachusetts, Amherst

    2010-01-01

    Catalytic hydrogenation of acetic acid to ethanol has been carried out in aqueous phase on several metals, with ruthenium being the most active and selective. DFT calculations suggest that the initial CO bond scission yielding acetyl is the key step and that the intrinsic reactivity of the metals accounts for the observed activity.

  10. PHASE ANALYSIS AND CRYSTAL STRUCTURE STUDIES ON BINARY ALLOYS OF ALUMINUM WITH TRANSITION METALS.

    Science.gov (United States)

    In order to provide the necessary background for detailed crystal-chemistry studies in the field of binary aluminum - transition metal systems, extensive investigations have been carried out on the phase relations of a large number of such systems. The results of these studies are briefly summarized, as are also the results of crystal structure determinations of a few alumi num - transition metal phases. (Author)

  11. Sulfate Resistance of Alkali Activated Pozzolans

    OpenAIRE

    Bondar, Dali

    2015-01-01

    The consequence of sulfate attack on geopolymer concrete, made from an alkali activated natural pozzolan (AANP) has been studied in this paper. Changes in the compressive strength, expansion and capillary water absorption of specimens have been investigated combined with phases determination by means of X-ray diffraction. At the end of present investigation which was to evaluate the performance of natural alumina silica based geopolymer concrete in sodium and magnesium sulfate solution, the l...

  12. Thermochemical analysis of laterite ore alkali roasting: Comparison of sodium carbonate, sodium sulfate, and sodium hydroxide

    Science.gov (United States)

    Samadhi, Tjokorde Walmiki

    2017-01-01

    The abundance of global nickel reserve is in fact dominated by low grade laterite ores containing only approximately 1.0-1.8 %-Ni. Indonesia is a major limonite and saprolite ores source, particularly in the Sulawesi, northern Maluku, and Papua islands. Production of nickel from laterites typically requires a pre-concentration step which breaks down the mineral crystalline structure, thereby facilitating the subsequent extraction of the valuable metals. This work discusses the thermochemical analysis of the alkali roasting of an Indonesian saprolite ore using Na2CO3, Na2SO4, and NaOH. These alkali compounds are selected due to their relatively low cost. The Factsage thermochemical computation package is used to predict thermodynamically stable gaseous, solution, pure liquid, and pure solid phases present in the roasting process at temperatures from 100 to 1200°C at ambient pressure, in inert atmosphere. The formation of a liquid solution (or slag) phase is interpreted as a major indicator of mineral structure breakdown. The computed slag formation temperatures are 373.2, 1041.4, and 792.0°C when using Na2CO3, Na2SO4, and NaOH, respectively. The masses of volatilized alkali at 1200°C with a total feed mass of 100 gram are 0.49, 3.24, and 3.25 mg for Na2CO3, Na2SO4, and NaOH, respectively. It is therefore hypothesized that Na2CO3 is the most competitive sodium-based alkali for saprolite ore roasting.

  13. Relation between the electroforming voltage in alkali halide-polymer diodes and the bandgap of the alkali halide

    Energy Technology Data Exchange (ETDEWEB)

    Bory, Benjamin F.; Wang, Jingxin; Janssen, René A. J.; Meskers, Stefan C. J., E-mail: s.c.j.meskers@tue.nl [Molecular Materials and Nanosystems and Institute for Complex Molecular Systems, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven (Netherlands); Gomes, Henrique L. [Instituto de Telecomunicações, Av. Rovisco, Pais 1, 1049-001 Lisboa, Portugal and Universidade do Algarve, Campus de Gambelas, 8005-139 Faro (Portugal); De Leeuw, Dago M. [Max-Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany and King Abdulaziz University, Jeddah (Saudi Arabia)

    2014-12-08

    Electroforming of indium-tin-oxide/alkali halide/poly(spirofluorene)/Ba/Al diodes has been investigated by bias dependent reflectivity measurements. The threshold voltages for electrocoloration and electroforming are independent of layer thickness and correlate with the bandgap of the alkali halide. We argue that the origin is voltage induced defect formation. Frenkel defect pairs are formed by electron–hole recombination in the alkali halide. This self-accelerating process mitigates injection barriers. The dynamic junction formation is compared to that of a light emitting electrochemical cell. A critical defect density for electroforming is 10{sup 25}/m{sup 3}. The electroformed alkali halide layer can be considered as a highly doped semiconductor with metallic transport characteristics.

  14. Efficient Preparation of Metal Organosols by Phase Transfer

    Institute of Scientific and Technical Information of China (English)

    ZHAO Ji-Kuan; CHEN Xiao; YANG Chun-Jie; SUI Zhen-Ming; ZHANG Guo-Dong; CHAI Yong-Cun; LIU Jie

    2005-01-01

    Organosols of silver and gold nanoparticles stabilized by sodium oleate were prepared with high efficiency by simple phase transfer of their hydrosols to isooctane. Concentrations of sodium oleate and magnesium chloride have crucial effects on the phase transfer efficiency. UV-visible absorption spectroscopy and transmission electron microscopy have been used to characterize the nanoparticles. A possible phase transfer mechanism was proposed based on the anchoring positions of oleate deduced by molecular modeling calculations.

  15. Crystal phase competition by addition of a second metal cation in solid solution metal-organic frameworks.

    Science.gov (United States)

    Castillo-Blas, C; Snejko, N; de la Peña-O'Shea, V A; Gallardo, J; Gutiérrez-Puebla, E; Monge, M A; Gándara, F

    2016-03-14

    Herein we report a synthetic study focused on the preparation of solid-solution metal-organic frameworks, MOFs, with the use of two kinds of linkers. In particular, we have explored the system composed by zinc, cobalt, 1,2,4-triazole and 4,4′-hexafluoroisopropylidenebisbenzoic acid (H2hfipbb). During this study, four new MOFs have been isolated, denoted TMPF-88 [M3(hfipbb)2(triazole)2(H2O)], TMPF-90 [M2(triazole)3(OCH2CH3)], TMPF-91 [M2(hfipbb)(triazole)2(H2O)] and TMPF-95 [M5(hfipbb)4(triazole)2(H2O)] (TMPF = transition metal polymeric framework, M = Zn, Co, or mixture of them). The study demonstrates that the addition of a second metal element during the MOF synthesis has a major effect in the formation of new phases, even at very high Zn/Co metal ratios. Furthermore, we show that during the MOF formation reaction, there is a competition among different crystal phases, where kinetically favoured phases of various compositions crystallize in short reaction times, precluding the formation of the pure solid-solution phases of other energetically more stable MOFs.

  16. New Alkali-Metal- and 2-Phenethylamine-Intercalated Superconductors Ax(C8H11N)yFe1-zSe (A = Li, Na) with the Largest Interlayer Spacings and Tc ˜ 40 K

    Science.gov (United States)

    Hatakeda, Takehiro; Noji, Takashi; Sato, Kazuki; Kawamata, Takayuki; Kato, Masatsune; Koike, Yoji

    2016-10-01

    New FeSe-based intercalation superconductors, Ax(C8H11N)yFe1-zSe (A = Li, Na), with Tc = 39-44 K have been successfully synthesized via the intercalation of alkali metals and 2-phenethylamine into FeSe. The interlayer spacings, namely, the distances between neighboring Fe layers, d, of Ax(C8H11N)yFe1-zSe (A = Li, Na) are 19.04(6) and 18.0(1) Å, respectively. These d values are the largest among those of the FeSe-based intercalation compounds and are understood to be due to the intercalation of two molecules of 2-phenethylamine in series perpendicular to the FeSe layers. It appears that the relationship between Tc and d in the FeSe-based intercalation superconductors is not domic but Tc is saturated at ˜45 K, which is comparable to the Tc values of single-layer FeSe films, for d ≥ 9 Å.

  17. Competitive binding exchange between alkali metal ions (K+, Rb+, and Cs+) and Na+ ions bound to the dimeric quadruplex [d(G4T4G4)]2: a 23Na and 1H NMR study.

    Science.gov (United States)

    Cesare Marincola, Flaminia; Virno, Ada; Randazzo, Antonio; Mocci, Francesca; Saba, Giuseppe; Lai, Adolfo

    2009-12-01

    A comparative study of the competitive cation exchange between the alkali metal ions K+, Rb+, and Cs+ and the Na+ ions bound to the dimeric quadruplex [d(G4T4G4)]2 was performed in aqueous solution by a combined use of the 23Na and 1H NMR spectroscopy. The titration data confirm the different binding affinities of these ions for the G-quadruplex and, in particular, major differences in the behavior of Cs+ as compared to the other ions were found. Accordingly, Cs+ competes with Na+ only for the binding sites at the quadruplex surface (primarily phosphate groups), while K+ and Rb+ are also able to replace sodium ions located inside the quadruplex. Furthermore, the 1H NMR results relative to the CsCl titration evidence a close approach of Cs+ ions to the phosphate groups in the narrow groove of [d(G4T4G4)]2. Based on a three-site exchange model, the 23Na NMR relaxation data lead to an estimate of the relative binding affinity of Cs+ versus Na+ for the quadruplex surface of 0.5 at 298 K. Comparing this value to those reported in the literature for the surface of the G-quadruplex formed by 5'-guanosinemonophosphate and for the surface of double-helical DNA suggests that topology factors may have an important influence on the cation affinity for the phosphate groups on DNA.

  18. Alkali-activated cementitious materials: Mechanisms, microstructure and properties

    Science.gov (United States)

    Jiang, Weimin

    The goal of this study was to examine the activation reaction, microstructure, properties, identify the mechanisms of activation, and achieve an enhanced understanding of activation processes occurring during the synthesis of alkali activated cementitious materials (AAC). The discussions classify the following categories. (1) alkali activated slag cement; (2) alkali activated portland-slag cement; (3) alkali activated fly ash-slag cement; (4) alkali activated pozzolana-lime cement; (5) alkali activated pozzolana cement. The activators involved are NaOH, KOH; Nasb2SOsb4;\\ Nasb2COsb3;\\ CaSOsb4, and soluble silicate of sodium and potassium. The effect of alkali activation on the microstructure of these materials were analyzed at the micro-nanometer scale by SEM, EDS, ESEM, and TEM. Also sp{29}Si and sp{27}Al MAS-NMR, IR, Raman, TGA, and DTA were performed to characterize the phase in these systems. Slag, fly ash, silica fume, as well as blended cements containing mixtures of these and other components were characterized. A set of ordinary portland cement paste samples served as a control. This study confirmed that AAC materials have great potential because they could generate very early high strength, greater durability and high performance. Among the benefits to be derived from this research is a better understanding of the factors that control concrete properties when using AAC materials, and by controlling the chemistry and processing to produce desired microstructures and properties, as well as their durability.

  19. The calcium-alkali syndrome

    OpenAIRE

    Arroyo, Mariangeli; Fenves, Andrew Z.; Emmett, Michael

    2013-01-01

    The milk-alkali syndrome was a common cause of hypercalcemia, metabolic alkalosis, and renal failure in the early 20th century. It was caused by the ingestion of large quantities of milk and absorbable alkali to treat peptic ulcer disease. The syndrome virtually vanished after introduction of histamine-2 blockers and proton pump inhibitors. More recently, a similar condition called the calcium-alkali syndrome has emerged as a common cause of hypercalcemia and alkalosis. It is usually caused b...

  20. Electron spin resonance study of electron localization and dynamics in metal-molten salt solutions: comparison of M-MX and Ln-LnX sub 3 melts (M alkali metal, Ln = rare earth metal, X = halogen)

    CERN Document Server

    Terakado, O; Freyland, W

    2003-01-01

    We have studied the electron spin resonance (ESR) spectra in liquid K-KCl and M-(NaCl/KCl) sub e sub u sub t mixtures at different concentrations in salt-rich melts approaching the metal-nonmetal transition region. In both systems F-centre-like characteristics are found. Strongly exchange narrowed signals clearly indicate that fast electron exchange occurs on the picosecond timescale. In contrast, the ESR spectra of a (NdCl sub 2)(NdCl sub 3)-(LiCl/KCl) sub e sub u sub t melt are characterized by a large line width of the order of 10 sup 2 mT which decreases with increasing temperature. In this case, the g-factor and correlation time are consistent with the model of intervalence charge transfer, which is supported by recent conductivity and optical measurements. The different transport mechanisms will be discussed.

  1. Measuring the noble metal and iodine composition of extracted noble metal phase from spent nuclear fuel using instrumental neutron activation analysis.

    Science.gov (United States)

    Palomares, R I; Dayman, K J; Landsberger, S; Biegalski, S R; Soderquist, C Z; Casella, A J; Brady Raap, M C; Schwantes, J M

    2015-04-01

    Masses of noble metal and iodine nuclides in the metallic noble metal phase extracted from spent fuel are measured using instrumental neutron activation analysis. Nuclide presence is predicted using fission yield analysis, and radionuclides are identified and the masses quantified using neutron activation analysis. The nuclide compositions of noble metal phase derived from two dissolution methods, UO2 fuel dissolved in nitric acid and UO2 fuel dissolved in ammonium-carbonate and hydrogen-peroxide solution, are compared.

  2. Studies of high temperature ternary phases in mixed-metal-rich early transition metal sulfide and phosphide systems

    Energy Technology Data Exchange (ETDEWEB)

    Marking, G.A.

    1994-01-04

    Investigations of ternary mixed early transition metal-rich sulfide and phosphide systems resulted in the discovery of new structures and new phases. A new series of Zr and Hf - group V transition metal - sulfur K-phases was synthesized and crystallographically characterized. When the group V transition metal was Nb or Ta, the unit cell volume was larger than any previously reported K-phase. The presence of adventitious oxygen was determined in two K-phases through a combination of neutron scattering and X-ray diffraction experiments. A compound Hf{sub 10}Ta{sub 3}S{sub 3} was found to crystallize in a new-structure type similar to the known gamma brasses. This structure is unique in that it is the only reported {open_quotes}stuffed{close_quotes} gamma-brass type structure. The metal components, Hf and Ta, are larger in size and more electropositive than the metals found in normal gamma brasses (e.g. Cu and Zn) and because of the larger metallic radii, sulfur can be incorporated into the structure where it plays an integral role in stabilizing this phase relative to others. X-ray single-crystal, X-ray powder and neutron powder refinements were performed on this structure. A new structure was found in the ternary Nb-Zr-P system which has characteristics in common with many known early transition metal-rich sulfides, selenides, and phosphides. This structure has the simplest known interconnection of the basic building blocks known for this structural class. Anomalous scattering was a powerful tool for differentiating between Zr and Nb when using Mo K{alpha} X-radiation. The compounds ZrNbP and HfNbP formed in the space group Prima with the simple Co{sub 2}Si structure which is among the most common structures found for crystalline solid materials. Solid solution compounds in the Ta-Nb-P, Ta-Zr-P, Nb-Zr-P, Hf-Nb-P, and Hf-Zr-S systems were crystallographically characterized. The structural information corroborated ideas about bonding in metal-rich compounds.

  3. Liquid Phase 3D Printing for Quickly Manufacturing Metal Objects with Low Melting Point Alloy Ink

    CERN Document Server

    Wang, Lei

    2014-01-01

    Conventional 3D printings are generally time-consuming and printable metal inks are rather limited. From an alternative way, we proposed a liquid phase 3D printing for quickly making metal objects. Through introducing metal alloys whose melting point is slightly above room temperature as printing inks, several representative structures spanning from one, two and three dimension to more complex patterns were demonstrated to be quickly fabricated. Compared with the air cooling in a conventional 3D printing, the liquid-phase-manufacturing offers a much higher cooling rate and thus significantly improves the speed in fabricating metal objects. This unique strategy also efficiently prevents the liquid metal inks from air oxidation which is hard to avoid otherwise in an ordinary 3D printing. Several key physical factors (like properties of the cooling fluid, injection speed and needle diameter, types and properties of the printing ink, etc.) were disclosed which would evidently affect the printing quality. In addit...

  4. Phase coexistence and Mott metal-insulator transition in the doped Hubbard-Holstein model

    Science.gov (United States)

    Moradi Kurdestany, Jamshid; Satpathy, Sashi

    2015-03-01

    Motivated by recent progress in the understanding of the Mott insulators away from half filling [?], often observed in the oxide materials, we study the role of the electron-lattice interaction vis-à-vis the electron correlations by studying the one-band Hubbard-Holstein model using the Gutzwiller variational method. Our theory predicts phase separation for sufficiently strong electron-lattice interaction, which however is frustrated in the solid due to the long-range Coulomb interaction of the dopant atoms, resulting in puddles of metallic phases embedded in the insulating matrix. Metallic state occurs when the volume fraction of the metallic phase exceeds the percolation threshold, as the dopant concentration is increased. Connection is made with the experimentally observed metal-insulator transition in the complex oxides.

  5. Thermodynamic properties and mixing thermodynamic parameters of two-phase metallic melts

    Institute of Scientific and Technical Information of China (English)

    Jian Zhang

    2005-01-01

    Based on the calculating model of metallic melts involving eutectic, the calculating equations of mixing thermodynamic parameters for two phase metallic melts have been formulated in the light of those equations of homogeneous solutions. Irrespective as to whether the activity deviation relative to Raoultian behavior is positive or negative, or the deviation is symmetrical or unsymmetrical, the evaluated results not only agree well with experimental values, but also strictly obey the mass action law. This testifies that these equations can authentically reflect the structural reality and mixing thermodynamic characteristics of two-phase metallic melts. The calculating equations of mixing thermodynamic parameters for the model of two phase metallic melts offer two practical criteria (activity and mixing thermodynamic parameters) and one theoretical criterion (the mass action law).

  6. Alkali Aggregate Reaction in Alkali Slag Cement Mortars

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    By means of "Mortar Bar Method",the ratio of cement to aggregate was kept as a constant 1∶2.25,the water-cement ratio of the mixture was 0.40,and six prism specimens were prepared for each batch of mixing proportions with dimensions of 10×10×60mm3 at 38±2℃ and RH≥95%, the influences of content and particle size of active aggregate, sort and content of alkali component and type of slag on the expansion ratios of alkali-activated slag cement(ASC) mortars due to alkali aggregate reaction(AAR) were studied. According to atomic absorption spectrometry,the amount of free alkali was measured in ASC mortars at 90d.The results show above factors affect AAR remarkably,but no dangerous AAR will occur in ASC system when the amount of active aggregate is below 15% and the mass fraction of alkali is not more than 5% (Na2O).Alkali participated in reaction as an independent component, and some hydrates containing alkali cations were produced, free alkalis in ASC system can be reduced enormously.Moreover,slag is an effective inhibitor, the possibility of generating dangerous AAR in ASC system is much lower at same conditions than that in ordinary Portland cement system.

  7. Natural Alkali Shifts to the Methanol Business

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    @@ Inner Mongolia Yuanxing Natural Alkali Co., Ltd. (Natural Alkali SZ: 000683) established in 1997 is a large chemical enterprise with new energy as its leading business and natural gas chemicals and natural alkali chemicals as the supplement business.

  8. Switching Characteristics of Phase Change Memory Cell Integrated with Metal-Oxide Semiconductor Field Effect Transistor

    Institute of Scientific and Technical Information of China (English)

    XU Cheng; CHEN Bomy; LIU Bo; CHEN Yi-Feng; LIANG Shuang; SONG Zhi-Tang; FENG Song-Lin; WAN Xu-Dong; YANG Zuo-Ya; XIE Joseph

    2008-01-01

    A Ge2Sb2Te5 based phase change memory device cell integrated with metal-oxide semiconductor field effect transistor (MOSFET) is fabricated using standard 0.18 μm complementary metal-oxide semiconductor process technology.It shows steady switching characteristics in the dc current-voltage measurement.The phase changing phenomenon from crystalline state to amorphous state with a voltage pulse altitude of 2.0 V and pulse width of 50 ns is also obtained.These results show the feasibility of integrating phase change memory cell with MOSFET.

  9. Holographic entanglement entropy in metal/superconductor phase transition with exponential nonlinear electrodynamics

    Science.gov (United States)

    Yao, Weiping; Jing, Jiliang

    2016-08-01

    We study the holographic entanglement entropy in metal/superconductor phase transition with exponential nonlinear electrodynamics (ENE) in four and five dimensional spacetimes. We find that the holographic entanglement entropy is powerful tool in studying the properties of the holographic phase transition. For the operator , we show that the entanglement entropy in 4-dimensional spacetime decreases in metal phase but changes non-monotonously in superconducting phase with the increase of the ENE parameter. Interestingly, the change of the entanglement entropy in 5-dimensional spacetime for the two phases is monotonous as the ENE factor alters. For the operator , we note that the behavior of entanglement entropy in four and five dimensional spacetimes changes monotonously for the two phases as we tune the strength of the ENE. Furthermore, for both operators, the entanglement entropy in four or five dimensional black hole increases with the increase of the width of the region.

  10. A metallic glass composite: Phase-field simulations and experimental analysis of microstructure evolution

    Energy Technology Data Exchange (ETDEWEB)

    Nestler, B. [Applied Research Center, Karlsruhe University of Applied Sciences, Moltkestrasse 30, D-76133 Karlsruhe (Germany)], E-Mail: britta.nestler@hs-karlsruhe.de; Danilov, D. [Applied Research Center, Karlsruhe University of Applied Sciences, Moltkestrasse 30, D-76133 Karlsruhe (Germany); Bracchi, A. [IV. Physikalisches Institut der Georg-August-Universitaet Goettingen, Friedrich-Hund-Platz 1, D-37077 Goettingen (Germany); Huang, Y.-L. [IV. Physikalisches Institut der Georg-August-Universitaet Goettingen, Friedrich-Hund-Platz 1, D-37077 Goettingen (Germany); Niermann, T. [IV. Physikalisches Institut der Georg-August-Universitaet Goettingen, Friedrich-Hund-Platz 1, D-37077 Goettingen (Germany); Seibt, M. [IV. Physikalisches Institut der Georg-August-Universitaet Goettingen, Friedrich-Hund-Platz 1, D-37077 Goettingen (Germany); Schneider, S. [IV. Physikalisches Institut der Georg-August-Universitaet Goettingen, Friedrich-Hund-Platz 1, D-37077 Goettingen (Germany)

    2007-04-15

    The growth process of a crystalline dendritic solid phase from an undercooled melt in the metallic glass composite Zr-Ti-Nb-Ni-Cu-Be is analyzed by experimental investigations and by adaptive finite element simulations based on a multicomponent phase-field model. The phase transition: L(liquid){yields}S(dendrite)+M(matrix) can be described by considering a pseudo-ternary system of late transition metals A=(Zr, Ti, Nb), of early transition metals B=(Ni, Cu) and of the component C=(Be). Scanning and transmission electron microscopy are employed to experimentally determine structural properties of the two-phase system and to provide concentration distributions of the components across the dendrite/matrix interface. The computed and experimentally observed microstructures, length scales and chemical compositions are in good agreement.

  11. Orbital Feshbach Resonance in Alkali-Earth Atoms.

    Science.gov (United States)

    Zhang, Ren; Cheng, Yanting; Zhai, Hui; Zhang, Peng

    2015-09-25

    For a mixture of alkali-earth atomic gas in the long-lived excited state ^{3}P_{0} and the ground state ^{1}S_{0}, in addition to nuclear spin, another "orbital" index is introduced to distinguish these two internal states. In this Letter we propose a mechanism to induce Feshbach resonance between two atoms with different orbital and nuclear spin quantum numbers. Two essential ingredients are the interorbital spin-exchange process and orbital dependence of the Landé g factors. Here the orbital degrees of freedom plays a similar role as the electron spin degree of freedom in magnetic Feshbach resonance in alkali-metal atoms. This resonance is particularly accessible for the ^{173}Yb system. The BCS-BEC crossover in this system requires two fermion pairing order parameters, and displays a significant difference compared to that in an alkali-metal system.

  12. Phase diagrams of microemulsions containing reducing agents and metal salts as bases for the synthesis of metallic nanoparticles.

    Science.gov (United States)

    Najjar, Reza; Stubenrauch, Cosima

    2009-03-01

    We studied the phase diagrams of microemulsions with a view to using these systems for the synthesis of metallic Pt, Pb, and Bi nanoparticles as well as of intermetallic Pt/Pb and Pt/Bi nanoparticles. The microemulsions consisted of H(2)O/salt-n-decane-SDS-1-butanol. The salt was either one metal precursor (H(2)PtCl(6) x 6 H(2)O, Pb(NO(3))(2), or Bi(NO(3))(3) x 5 H(2)O), a mixture of two metal precursors (H(2)PtCl(6) x 6 H(2)O + Pb(NO(3))(2) or H(2)PtCl(6) x 6 H(2)O + Bi(NO(3))(3) x 5 H(2)O), or the reducing agent (NaBH(4)). In addition, other salts needed to be added in order to solubilize the metal precursors, to stabilize the reducing agent, and to adjust the ionic strength. Combining the microemulsion (mu e1) that contains the metal precursor(s) with the microemulsion (mu e2) that contains the reducing agent leads to metallic nanoparticles. To study systematically how the shape and size of the synthesized metallic nanoparticles depend on the size and shape of the respective microemulsion droplets, first of all one has to find those conditions under which mu e1 and mu e2 have the same structure. For that purpose we determined the water emulsification failure boundary (wefb) of each microemulsion as it is at the wefb where the water droplets are known to be spherical. We found that the ionic strength (I) of the aqueous phase as well as the hard acid and hard base properties of the ions are the key tuning parameters for the location of the wefb.

  13. Phase stability in heavy f-electron metals from first-principles theory

    Energy Technology Data Exchange (ETDEWEB)

    Soderlind, P

    2005-11-17

    The structural phase stability of heavy f-electron metals is studied by means of density-functional theory (DFT). These include temperature-induced transitions in plutonium metal as well as pressure-induced transitions in the trans-plutonium metals Am, Cm, Bk, and Cf. The early actinides (Th-Np) display phases that could be rather well understood from the competition of a crystal-symmetry breaking mechanism (Peierls distortion) of the 5f states and electrostatic forces, while for the trans-plutonium metals (Am-Cf) the ground-state structures are governed by 6d bonding. We show in this paper that new physics is needed to understand the phases of the actinides in the volume range of about 15-30 {angstrom}{sup 3}. At these volumes one would expect, from theoretical arguments made in the past, to encounter highly complex crystal phases due to a Peierls distortion. Here we argue that the symmetry reduction associated with spin polarization can make higher symmetry phases competitive. Taking this into account, DFT is shown to describe the well-known phase diagram of plutonium and also the recently discovered complex and intriguing high-pressure phase diagrams of Am and Cm. The theory is further applied to investigate the behaviors of Bk and Cf under compression.

  14. Structures and Nonlinear Optical Properties of Alkali Metal-Doped t-Bu-calix[4]arene Molecules%碱金属掺杂叔丁基杯[4]芳烃体系的结构及非线性光学性质

    Institute of Scientific and Technical Information of China (English)

    侯娜; 李莹; 吴迪; 李志儒

    2014-01-01

    采用密度泛函理论B3LYP方法得到了M@t-Bu-calix[4]arene和(M@t-Bu-calix[4]arene)Li′(M=Li, Na, K)体系的几何结构.其中(M@t-Bu-calix[4]arene)Li′(M=Li, Na, K)三个体系各有5个稳定异构体,在前三个异构体中,碱金属与t-Bu-calix[4]arene分子间具有很强的相互作用能,说明了体系的稳定性.在部分(M@t-Bu-calix[4]arene)Li异构体中Li′原子以阴离子形式存在,整个体系表现出碱金属化物的特性.此外,使用CAM-B3LYP方法计算了t-Bu-calix[4]arene及碱金属掺杂后体系的非线性光学性质.结果表明, t-Bu-calix[4]arene内部掺杂一个碱金属原子M后,体系的一阶超极化率(β0)有较大提高,而在配体外部又掺杂一个Li原子后,体系具有更大的β0值.其中(M@t-Bu-calix[4]arene)Li′体系的MLi′-4异构体表现出最高的β0值(41827-114354 a.u.),并且随着M原子序数的增加而逐渐增大.可见,碱金属掺杂是提高t-Bu-calix[4]arene非线性光学响应的一种有效策略.%Using density functional theory with the B3LYP functional, the optimized geometrical structures of the M@t-Bu-calix[4]arene and (M@t-Bu-calix[4]arene)Li′(M=Li, Na, K) compounds were obtained. Five stable isomers were identified for each bi-alkali-metal-doped (M@t-Bu-calix[4]arene)Li′species. The first three low-lying isomers have considerable intramolecular interaction energies between alkali metal atoms and the t-Bu-calix[4]arene molecule, indicating their stabilities. According to natural bond orbital analyses, the outside Li′atom is negatively charged in some (M@t-Bu-calix[4]arene)Li′structures, indicating the alkalide characteristics of these isomers. In addition, the nonlinear optical (NLO) properties of isolated and alkali-metal-doped t-Bu-calix [4]arene molecules were calculated using the CAM-B3LYP method. The results indicate that the single-doped effect of alkali metal M greatly enhances the first hyperpolarizability (β0) of the t-Bu-calix[4]arene molecule. In

  15. Generation of copper rich metallic phases from waste printed circuit boards

    Energy Technology Data Exchange (ETDEWEB)

    Cayumil, R. [Centre for Sustainable Materials Research and Technology (SMaRT), School of Materials Science and Engineering, The University of New South Wales, Sydney, NSW 2052 (Australia); Khanna, R., E-mail: ritakhanna@unsw.edu.au [Centre for Sustainable Materials Research and Technology (SMaRT), School of Materials Science and Engineering, The University of New South Wales, Sydney, NSW 2052 (Australia); Ikram-Ul-Haq, M.; Rajarao, R. [Centre for Sustainable Materials Research and Technology (SMaRT), School of Materials Science and Engineering, The University of New South Wales, Sydney, NSW 2052 (Australia); Hill, A. [CSIRO Process Science and Engineering, Clayton, Melbourne, VIC 3168 (Australia); Sahajwalla, V. [Centre for Sustainable Materials Research and Technology (SMaRT), School of Materials Science and Engineering, The University of New South Wales, Sydney, NSW 2052 (Australia)

    2014-10-15

    Highlights: • Recycling and material recovery from waste printed circuit boards is very complex. • Thermoset polymers, ceramics and metals are present simultaneously in waste PCBs. • Heat treatment of PCBs was carried out at 1150 °C under inert conditions. • Various metallic phases could be segregated out as copper based metallic droplets. • Carbon and ceramics residues can be further recycled in a range of applications. - Abstract: The rapid consumption and obsolescence of electronics have resulted in e-waste being one of the fastest growing waste streams worldwide. Printed circuit boards (PCBs) are among the most complex e-waste, containing significant quantities of hazardous and toxic materials leading to high levels of pollution if landfilled or processed inappropriately. However, PCBs are also an important resource of metals including copper, tin, lead and precious metals; their recycling is appealing especially as the concentration of these metals in PCBs is considerably higher than in their ores. This article is focused on a novel approach to recover copper rich phases from waste PCBs. Crushed PCBs were heat treated at 1150 °C under argon gas flowing at 1 L/min into a horizontal tube furnace. Samples were placed into an alumina crucible and positioned in the cold zone of the furnace for 5 min to avoid thermal shock, and then pushed into the hot zone, with specimens exposed to high temperatures for 10 and 20 min. After treatment, residues were pulled back to the cold zone and kept there for 5 min to avoid thermal cracking and re-oxidation. This process resulted in the generation of a metallic phase in the form of droplets and a carbonaceous residue. The metallic phase was formed of copper-rich red droplets and tin-rich white droplets along with the presence of several precious metals. The carbonaceous residue was found to consist of slag and ∼30% carbon. The process conditions led to the segregation of hazardous lead and tin clusters in the

  16. Room temperature oxidative intercalation with chalcogen hydrides: Two-step method for the formation of alkali-metal chalcogenide arrays within layered perovskites

    Energy Technology Data Exchange (ETDEWEB)

    Ranmohotti, K.G. Sanjaya; Montasserasadi, M. Dariush; Choi, Jonglak; Yao, Yuan; Mohanty, Debasish; Josepha, Elisha A.; Adireddy, Shiva; Caruntu, Gabriel [Department of Chemistry and the Advanced Materials Research Institute, University of New Orleans, New Orleans, LA 70148-2820 (United States); Wiley, John B., E-mail: jwiley@uno.edu [Department of Chemistry and the Advanced Materials Research Institute, University of New Orleans, New Orleans, LA 70148-2820 (United States)

    2012-06-15

    Highlights: ► Topochemical reactions involving intercalation allow construction of metal chalcogenide arrays within perovskite hosts. ► Gaseous chalcogen hydrides serve as effect reactants for intercalation of sulfur and selenium. ► New compounds prepared by a two-step intercalation strategy are presented. -- Abstract: A two-step topochemical reaction strategy utilizing oxidative intercalation with gaseous chalcogen hydrides is presented. Initially, the Dion-Jacobson-type layered perovskite, RbLaNb{sub 2}O{sub 7}, is intercalated reductively with rubidium metal to make the Ruddlesden-Popper-type layered perovskite, Rb{sub 2}LaNb{sub 2}O{sub 7}. This compound is then reacted at room-temperature with in situ generated H{sub 2}S gas to create Rb-S layers within the perovskite host. Rietveld refinement of X-ray powder diffraction data (tetragonal, a = 3.8998(2) Å, c = 15.256(1) Å; space group P4/mmm) shows the compound to be isostructural with (Rb{sub 2}Cl)LaNb{sub 2}O{sub 7} where the sulfide resides on a cubic interlayer site surrounded by rubidium ions. The mass increase seen on sulfur intercalation and the refined S site occupation factor (∼0.8) of the product indicate a higher sulfur content than expected for S{sup 2−} alone. This combined with the Raman studies, which show evidence for an H-S stretch, indicate that a significant fraction of the intercalated sulfide exists as hydrogen sulfide ion. Intercalation reactions with H{sub 2}Se{sub (g)} were also carried out and appear to produce an isostructural selenide compound. The utilization of such gaseous hydride reagents could significantly expand multistep topochemistry to a larger number of intercalants.

  17. Pair natural orbital and canonical coupled cluster reaction enthalpies involving light to heavy alkali and alkaline earth metals: the importance of sub-valence correlation

    KAUST Repository

    Minenkov, Yury

    2017-03-07

    In this work, we tested canonical and domain based pair natural orbital coupled cluster methods (CCSD(T) and DLPNO-CCSD(T), respectively) for a set of 32 ligand exchange and association/dissociation reaction enthalpies involving ionic complexes of Li, Be, Na, Mg, Ca, Sr, Ba and Pb(ii). Two strategies were investigated: in the former, only valence electrons were included in the correlation treatment, giving rise to the computationally very efficient FC (frozen core) approach; in the latter, all non-ECP electrons were included in the correlation treatment, giving rise to the AE (all electron) approach. Apart from reactions involving Li and Be, the FC approach resulted in non-homogeneous performance. The FC approach leads to very small errors (<2 kcal mol-1) for some reactions of Na, Mg, Ca, Sr, Ba and Pb, while for a few reactions of Ca and Ba deviations up to 40 kcal mol-1 have been obtained. Large errors are both due to artificial mixing of the core (sub-valence) orbitals of metals and the valence orbitals of oxygen and halogens in the molecular orbitals treated as core, and due to neglecting core-core and core-valence correlation effects. These large errors are reduced to a few kcal mol-1 if the AE approach is used or the sub-valence orbitals of metals are included in the correlation treatment. On the technical side, the CCSD(T) and DLPNO-CCSD(T) results differ by a fraction of kcal mol-1, indicating the latter method as the perfect choice when the CPU efficiency is essential. For completely black-box applications, as requested in catalysis or thermochemical calculations, we recommend the DLPNO-CCSD(T) method with all electrons that are not covered by effective core potentials included in the correlation treatment and correlation-consistent polarized core valence basis sets of cc-pwCVQZ(-PP) quality.

  18. Effects of metal ion adduction on the gas-phase conformations of protein ions.

    Science.gov (United States)

    Flick, Tawnya G; Merenbloom, Samuel I; Williams, Evan R

    2013-11-01

    Changes in protein ion conformation as a result of nonspecific adduction of metal ions to the protein during electrospray ionization (ESI) from aqueous solutions were investigated using traveling wave ion mobility spectrometry (TWIMS). For all proteins examined, protein cations (and in most cases anions) with nonspecific metal ion adducts are more compact than the fully protonated (or deprotonated) ions with the same charge state. Compaction of protein cations upon nonspecific metal ion binding is most significant for intermediate charge state ions, and there is a greater reduction in collisional cross section with increasing number of metal ion adducts and increasing ion valency, consistent with an electrostatic interaction between the ions and the protein. Protein cations with the greatest number of adducted metal ions are no more compact than the lowest protonated ions formed from aqueous solutions. These results show that smaller collisional cross sections for metal-attached protein ions are not a good indicator of a specific metal-protein interaction in solution because nonspecific metal ion adduction also results in smaller gaseous protein cation cross sections. In contrast, the collisional cross section of α-lactalbumin, which specifically binds one Ca(2+), is larger for the holo-form compared with the apo-form, in agreement with solution-phase measurements. Because compaction of protein cations occurs when metal ion adduction is nonspecific, elongation of a protein cation may be a more reliable indicator that a specific metal ion-protein interaction occurs in solution.

  19. New alkali metal diphosphates how materials to preserve the security of the environment: CsNaCu(P2O7), Rb2Cu(P2O7) and CsNaCo(P2O7) synthesis and crystal structure determination

    Science.gov (United States)

    Chernyatieva, Anastasiya; Filatova, Alyona; Spiridonova, Dariya; Krivovichev, Sergey

    2013-04-01

    In this work we describe preliminary results of the synthesis and of a crystal-chemical study of synthetic phosphates with transition metals. Due to the increasing requirements for environmental safety specialists from various industries, we are searching for sustainable forms of immobilization of hazardous waste during storage. We are also developing a component-based waste for new materials. In our continued exploratory synthesis of compounds containing transition-metals, we were able to produce the new diphosphate phases CsNaCu(P2O7), Rb2Cu(P2O7) and CsNaCo(P2O7). A crystal chemical study has allowed us to identify new phosphates. Crystals of CsNaCu(P2O7) (Phase 1) is orthorhombic, crystallizes in space group Pmn21, with a = 5.147(8), b = 15.126(2), c = 9.717(2) Å, V = 756.20 Å3, R1 = 0.066 and Rb2Cu(P2O7) (Phase 2) is orthorhombic as well, crystallizes in space group Pmcn, with a = 5.183(8), b = 10.096(1), c = 15.146(3) Å, V = 793.55 Å3, R1 = 0.063, they have been obtained by high-temperature reaction of RbNO3, CsNO3, Cu(NO3)2, NaOH and (NH4)4P2O7. Synthetic crystals of the phosphate of copper and rubidium were studied in detail by us on the structures of Rb2Cu(P2O7) and Rb2Cu3(P2O7)2 - new alkali metal copper diphosphates (CHERNYATIEVA et al., 2008). Here we report the synthesis, the structure and the properties of the title compounds and we compare these phases with the previously discovered K2CuP2O7 (ELMAADI et al., 1995) and CsNaMnP2O7 (HUANG et al., 1998). These structures crystallize in other space groups, although their structures are also based on 2-D layers, formed by P2O7 groups combined with polyhedra of the transition metals (CHERNYATIEVA et al., 2012). A crystal chemical study has allowed us to identify even new diphosphates CsNaCu(P2O7) (Phase 3). Crystals of CsNaCoP2O7 is monoclinic, space group P 21/n, with a = 7,424(2), b = 7,648(1), c = 12,931(3)Å, β = 90,71(2)° , V = 734.2(3) Å3 and R1 = 0.060. The structure is based framework of Co

  20. Why do high-redshift galaxies show diverse gas-phase metallicity gradients?

    CERN Document Server

    Ma, Xiangcheng; Feldmann, Robert; Torrey, Paul; Faucher-Giguere, Claude-Andre; Keres, Dusan

    2016-01-01

    Recent spatially resolved observations of galaxies at z=0.6-3 reveal that high-redshift galaxies show complex kinematics and a broad distribution of gas-phase metallicity gradients. To understand these results, we use a suite of high-resolution cosmological zoom-in simulations from the Feedback in Realistic Environments (FIRE) project, which include physically motivated models of the multi-phase ISM, star formation, and stellar feedback. Our simulations reproduce the observed diversity of kinematic properties and metallicity gradients, broadly consistent with observations at z=0-3. Strong negative metallicity gradients only appear in galaxies with a rotating disk, but not all rotationally supported galaxies have significant gradients. Strongly perturbed galaxies with little rotation always have flat gradients. The kinematic properties and metallicity gradient of a high-redshift galaxy can vary significantly on short time-scales, associated with starburst episodes. Feedback from a starburst can destroy the gas...

  1. Valorization of BOF Steel Slag by Reduction and Phase Modification: Metal Recovery and Slag Valorization

    Science.gov (United States)

    Liu, Chunwei; Huang, Shuigen; Wollants, Patrick; Blanpain, Bart; Guo, Muxing

    2017-03-01

    Basic oxygen furnace (BOF) steel slag is a main byproduct in steelmaking, and its valorization is therefore of considerable interest, from a metal-recovery perspective and from a residue-utilization perspective. In the present study, the carbothermic reduction of BOF slag was investigated systematically. The reductions of Fe- and P-containing phases (i.e., oxide and compounds) are discussed. Effects of Al2O3 and SiO2 additions on the solidification microstructure and mineralogy associated with the reduction processes were also investigated. The formation and growth of the extracted metallic phase are discussed, and the mineralogy of the residue slag is determined. We conclude that by controlling the additions under a rapid cooling condition, it is possible to extract metallic iron as high-grade metal and simultaneously to utilize the remaining slag for construction applications.

  2. Trace metals partitioning among different sedimentary mineral phases and the deposit-feeding polychaete Armandia brevis

    Energy Technology Data Exchange (ETDEWEB)

    Díaz-de-Alba, Margarita [Department of Analytical Chemistry, Institute of Biomolecules (INBIO), Faculty of Sciences, CEI-MAR, University of Cadiz, Campus Rio S. Pedro, E-11510, Puerto Real, Cadiz (Spain); Huerta-Diaz, Miguel Angel, E-mail: huertam@uabc.edu.mx [Instituto de Investigaciones Oceanológicas, Universidad Autónoma de Baja California, Campus Ensenada, Km. 103 Carr. Tijuana-Ensenada, Ensenada 22800, Baja California (Mexico); Delgadillo-Hinojosa, Francisco [Instituto de Investigaciones Oceanológicas, Universidad Autónoma de Baja California, Campus Ensenada, Km. 103 Carr. Tijuana-Ensenada, Ensenada 22800, Baja California (Mexico); Hare, Landis [Centre Eau Terre Environnement, 490, rue de la Couronne, Québec, Québec G1K 9A9 (Canada); Galindo-Riaño, M. Dolores [Department of Analytical Chemistry, Institute of Biomolecules (INBIO), Faculty of Sciences, CEI-MAR, University of Cadiz, Campus Rio S. Pedro, E-11510, Puerto Real, Cadiz (Spain); Siqueiros-Valencia, Arturo [Instituto de Investigaciones Oceanológicas, Universidad Autónoma de Baja California, Campus Ensenada, Km. 103 Carr. Tijuana-Ensenada, Ensenada 22800, Baja California (Mexico)

    2016-02-01

    Trace metals (Cd, Co, Cu, Fe, Mn, Ni, Pb, Zn) were determined in two operationally defined fractions (HCl and pyrite) in sediments from Ensenada and El Sauzal harbors (Mexico). The HCl fraction had significantly higher metal concentrations relative to the pyrite fraction in both harbors, underlining the weak tendency of most trace metals to associate with pyrite. Exceptionally, Cu was highly pyritized, with degrees of trace metal pyritization (DTMP) > 80% in both harbors. Dissolved Fe flux measurements combined with solid phase Fe sulfide data indicated that 98 mt of Fe are precipitated as iron sulfides every year in Ensenada Harbor. These Fe sulfides (and associated trace metals) will remain preserved in the sediments, unless they are perturbed by dredging or sediment resuspension. Calculations indicate that dredging activities could export to the open ocean 0.20 ± 0.13 to (0.30 ± 0.56) × 10{sup 3} mt of Cd and Cu, respectively, creating a potential threat to marine benthic organisms. Degrees of pyritization (DOP) values in Ensenada and El Sauzal harbors were relatively low (< 25%) while degrees of sulfidization (DOS) were high (~ 50%) because of the contribution of acid volatile sulfide. DOP values correlated with DTMP values (p ≤ 0.001), indicating that metals are gradually incorporated into pyrite as this mineral is formed. Significant correlations were also found between DTMP values and − log(K{sub sp(MeS)}/K{sub sp(pyr)}) for both harbors, indicating that incorporation of trace metals into the pyrite phase is a function of the solubility product of the corresponding metal sulfide. The order in which elements were pyritized in both harbors was Zn ≈ Mn < Fe < Cd ≈ Pb < Ni ≈ Co < < Cu. Lastly, a strong correlation (r{sup 2} = 0.87, p < 0.01) was found between average reactive trace metal concentrations and metal concentrations measured in Armandia brevis (a deposit-feeding Opheliid polychaete), suggesting that these labile sedimentary metals are

  3. Regularities of formation of ternary alloy phases between non-transition metals

    Institute of Scientific and Technical Information of China (English)

    姚莉秀; 陈瑞亮; 钦佩; 陈念贻; 陆文聪

    2000-01-01

    Using a four-parameter model based on extended Miedema’ s cellular model of alloy phases and pattern recognition methods, the regularities of formation of ternary intermetallic compounds between non-transition metals have been investigated. The criterion of formation can be expressed as some empirical functions of Φ (electronegativity), nws1/3( valence electron density in Wagn-er-Seitz cell), R (Pauling’s metallic radius) and Z (number of valence electrons in atom).

  4. Regularities of formation of ternary alloy phases between non-transition metals

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Using a four-parameter model based on extended Miedema's cellular model of alloy phases and pattern recognition methods, the regularities of formation of ternary intermetallic compounds between non-transition metals have been investigated. The criterion of formation can be expressed as some empirical functions of Ф (electronegativity), n1/3WS (valence electron density in Wagner-Seitz cell), R (Pauling's metallic radius) and Z (number of valence electrons in atom).

  5. Method and apparatus for selective capture of gas phase analytes using metal .beta.-diketonate polymers

    Science.gov (United States)

    Harvey, Scott D [Kennewick, WA

    2011-06-21

    A process and sensor device are disclosed that employ metal .beta.-diketonate polymers to selectively capture gas-phase explosives and weaponized chemical agents in a sampling area or volume. The metal .beta.-diketonate polymers can be applied to surfaces in various analytical formats for detection of: improvised explosive devices, unexploded ordinance, munitions hidden in cargo holds, explosives, and chemical weapons in public areas.

  6. Spectral descriptors for bulk metallic glasses based on the thermodynamics of competing crystalline phases

    CERN Document Server

    Perim, Eric; Liu, Yanhui; Toher, Cormac; Gong, Pan; Li, Yanglin; Simmons, W Neal; Levy, Ohad; Vlassak, Joost J; Schroers, Jan; Curtarolo, Stefano

    2016-01-01

    Metallic glasses have attracted considerable interest in recent years due to their unique combination of superb properties and processability. Predicting bulk metallic glass formers from known parameters remains a challenge and the search for new systems is still performed by trial and error. It has been speculated that some sort of "confusion" during crystallization of the crystalline phases competing with glass formation could play a key role. Here, we propose a heuristic descriptor quantifying confusion and demonstrate its validity by detailed experiments on two well-known glass forming alloy systems. With the insight provided by these results, we develop a robust model for predicting glass formation ability based on the spectral decomposition of geometrical and energetic features of crystalline phases calculated ab-initio in the AFLOW high throughput framework. Our findings indicate that the formation of metallic glass phases could be a much more common phenomenon than currently estimated, with more than ...

  7. Rich structural chemistry in new alkali metal yttrium tellurites: three-dimensional frameworks of NaYTe4O10, KY(TeO3)2, RbY(TeO3)2, and a novel variant of hexagonal tungsten bronze, CsYTe3O8.

    Science.gov (United States)

    Kim, Youngkwon; Lee, Dong Woo; Ok, Kang Min

    2015-01-05

    Pure polycrystalline phases and single crystals of four new quaternary alkali metal yttrium tellurites, NaYTe4O10, KY(TeO3)2, RbY(TeO3)2, and CsYTe3O8, have been prepared by solid-state and hydrothermal reactions using A2CO3 (A = Na, K, Rb, and Cs), Y(NO3)3·6H2O, Y2O3, and TeO2 as starting reagents. X-ray diffraction analyses suggest that NaYTe4O10 exhibits a highly symmetric three-dimensional (3D) framework consisting of YO8 square antiprisms and chains of TeO4 polyhedra. Within the framework, six- (6-) and eight-membered ring (8-MR) channels are observed. KY(TeO3)2 and RbY(TeO3)2 are isostructural to each other and reveal another 3D framework with structures containing YO6 octahedra and TeO3 trigonal pyramids with 4-MR and 12-MR channels. CsYTe3O8 shows a hexagonal tungsten bronze (HTB)-like topology composed of hexagonal tungsten oxide-like layers of TeO4 polyhedra and YO6 octahedral linkers with 3-MR and 6-MR channels. Thermal analyses, elemental analyses, and spectroscopic characterizations, such as UV-vis diffuse reflectance and infrared spectra, are presented, as are local dipole moment calculations for the constituent asymmetric polyhedra TeO3 and TeO4.

  8. Synthesis, Crystal Structure, and Nonlinear Optical Properties of a New Alkali and Alkaline Earth Metal Carbonate RbNa5Ca5(CO38

    Directory of Open Access Journals (Sweden)

    Qiaoling Chen

    2016-12-01

    Full Text Available A new nonlinear optical (NLO material, RbNa5Ca5(CO38, has been synthesized by the hydrothermal method. The crystal structure is established by single-crystal X-ray diffraction. RbNa5Ca5(CO38 crystallizes in the hexagonal crystal system with space group P63mc (No. 186. The structure of RbNa5Ca5(CO38 can be described as the adjacent infinite [CaCO3]∞ layers lying in the a-b plane bridged through standing-on-edge [CO3] groups by sharing O atoms (two-fold coordinated to build a framework with four types of tunnels running through the b-axis. The Rb, Na, and [Na0.67Ca0.33] atoms reside in these tunnels, respectively. The measurement of second harmonic generation (SHG indicated that RbNa5Ca5(CO38 is a phase-matchable material, which had SHG responses of approximately 1×KH2PO4 (KDP. Meanwhile, the results from the UV-VIS diffuse reflectance spectroscopy study of the powder samples indicated that the UV cut-off edges of RbNa5Ca5(CO38 is about 203 nm.

  9. High-resolution nanoprobe X-ray fluorescence characterization of heterogeneous calcium and heavy metal distributions in alkali-activated fly ash.

    Science.gov (United States)

    Provis, John L; Rose, Volker; Bernal, Susan A; van Deventer, Jannie S J

    2009-10-06

    The nanoscale distribution of elements within fly ash and the aluminosilicate gel products of its alkaline activation ("fly ash geopolymers") are analyzed by means of synchrotron X-ray fluorescence using a hard X-ray Nanoprobe instrument. The distribution of calcium within a hydroxide-activated (fly ash/KOH solution) geopolymer gel is seen to be highly heterogeneous, with these data providing for the first time direct evidence of the formation of discrete high-calcium particles within the binder structure of a geopolymer synthesized from a low-calcium (geopolymer gel binder structure surrounding the unreacted fly ash particles. This has important implications for the understanding of calcium chemistry within aluminosilicate geopolymer gel phases. Additionally, chromium and iron are seen to be very closely correlated within the structures of both fly ash and the geopolymer product and remain within the regions of the geopolymer which can be identified as unreacted fly ash particles. Given that the potential for chromium release has been one of the queries surrounding the widespread utilization of construction materials derived from fly ash, the observation that this element appears to be localized within the fly ash rather than dispersed throughout the gel binder indicates that it is unlikely to be released problematically into the environment.

  10. Spectroscopic characteristic (FT-IR, FT-Raman, UV, 1H and 13C NMR), theoretical calculations and biological activity of alkali metal homovanillates

    Science.gov (United States)

    Samsonowicz, M.; Kowczyk-Sadowy, M.; Piekut, J.; Regulska, E.; Lewandowski, W.

    2016-04-01

    The structural and vibrational properties of lithium, sodium, potassium, rubidium and cesium homovanillates were investigated in this paper. Supplementary molecular spectroscopic methods such as: FT-IR, FT-Raman in the solid phase, UV and NMR were applied. The geometrical parameters and energies were obtained from density functional theory (DFT) B3LYP method with 6-311++G** basis set calculations. The geometry of the molecule was fully optimized, vibrational spectra were calculated and fundamental vibrations were assigned. Geometric and magnetic aromaticity indices, atomic charges, dipole moments, HOMO and LUMO energies were also calculated. The microbial activity of investigated compounds was tested against Bacillus subtilis (BS), Pseudomonas aeruginosa (PA), Escherichia coli (EC), Staphylococcus aureus (SA) and Candida albicans (CA). The relationship between the molecular structure of tested compounds and their antimicrobial activity was studied. The principal component analysis (PCA) was applied in order to attempt to distinguish the biological activities of these compounds according to selected band wavenumbers. Obtained data show that the FT-IR spectra can be a rapid and reliable analytical tool and a good source of information for the quantitative analysis of the relationship between the molecular structure of the compound and its biological activity.

  11. Synthesis, structure and luminescence properties of phosphates A$_{1−3x}$Eu$_x$Zr$_2$(PO$_4$)$_3$ (A—alkali metal)

    Indian Academy of Sciences (India)

    ANTON KANUNOV; BENOIT GLORIEUX; ALBINA ORLOVA; ELENA BOROVIKOVA; GALINA ZAVEDEEVA

    2017-02-01

    The solid solution row A$_{1−3x}Eu$^{3+}_x$Zr$_2$(PO$_4$)$_3$, where $A= Na$, K, Rb, Cs and x ranging from 0 to 0.25 was obtained by methods based on sol–gel processes in the presence of the salting-out agent, C$_2$H$_5$OH. The formation of phases of the structural type NaZr$_2$(PO$_4$)$_3$ (NZP) and their crystallization in the crystal forms belonging to the space group $R\\bar{3}c$ ($0 \\le x \\le 0.1$) and $P\\bar{3}c$ ($x = 0.25$) were determined. Morphotropic transition occurred. Trivalent europium was included as a local probe. Its electric and magnetic dipole was used to characterize the substitutionrule and the localization of this cation in the structure, which is in agreement with the structural characterization. It appears that europium is located in the M1 and M2 sites as a function of the Eu$^{3+}$ concentration.

  12. Patterning of Nanocrystalline Cellulose Gel Phase by Electrodissolution of a Metallic Electrode

    Science.gov (United States)

    Daignan, Jean-Michel; Chen, Ran; Mahmoud, Khaled A.; Ma, Yuan; Hill, Ian G.; Kreplak, Laurent

    2014-01-01

    At high concentration or in the presence of electrolytes and organic solvents, solutions of cellulose nanocrystals (CNCs) can form gels exhibiting optical properties similar to the ones of liquid crystal phases. In an attempt to pattern such a gel phase, we have studied the electrodissolution of a metallic electrode in a water suspension of carboxylated CNCs (cCNCs). Depending on the metal used, the electrodissolution process was observed at a different positive potential. In the case of copper the minimum potential at which we could observe optically the growth of the gel phase was 200 mV. The growth rate was current limited indicating that the process was controlled by the electrodissolution of the copper electrode. This hypothesis was confirmed by using circular and square copper patterns as positive electrodes. In both cases, the consumption of the electrode material was observed optically and correlated with the growth of the gel phase. PMID:24897116

  13. Enhance luminescence by introducing alkali metal ions (R+ = Li+, Na+ and K+) in SrAl2O4:Eu3+ phosphor by solid-state reaction method

    Science.gov (United States)

    Prasad Sahu, Ishwar

    2016-05-01

    In the present article, the role of charge compensator ions (R+ = Li+, Na+ and K+) in europium-doped strontium aluminate (SrAl2O4:Eu3+) phosphors was synthesized by the high-temperature, solid-state reaction method. The crystal structures of sintered phosphors were in a monoclinic phase with space group P21. The trap parameters which are mainly activation energy (E), frequency factor (s) and order of the kinetics (b) were evaluated by using the peak shape method. The calculated trap depths are in the range from 0.76 to 0.84 eV. Photoluminescence measurements showed that the phosphor exhibited emission peak with good intensity at 595 nm, corresponding to 5D0-7F1 (514 nm) orange emission and weak 5D0-7F2 (614 nm) red emission. The excitation spectra monitored at 595 nm show a broad band from 220 to 320 nm ascribed to O-Eu charge-transfer state transition and the other peaks in the range of 350-500 nm originated from f-f transitions of Eu3+ ions. The strongest band at 394 nm can be assigned to 7F0-5L6 transition of Eu3+ ions due to the typical f-f transitions within Eu3+ of 4f6 configuration. The latter lies in near ultraviolet (350-500 nm) emission of UV LED. CIE color chromaticity diagram and thermoluminescence spectra confirm that the synthesized phosphors would emit an orange-red color. Incorporating R+ = Li+, Na+ and K+ as the compensator charge, the emission intensity of SrAl2O4:Eu3+ phosphor can be obviously enhanced and the emission intensity of SrAl2O4:Eu3+ doping Li+ is higher than that of Na+ or K+ ions.

  14. ALLOYING-DRIVEN PHASE STABILITY IN GROUP-VB TRANSITION METALS UNDER COMPRESSION

    Energy Technology Data Exchange (ETDEWEB)

    Landa, A; Soderlind, P

    2011-04-11

    The change in phase stability of Group-VB (V, Nb, and Ta) transition metals due to pressure and alloying is explored by means of first-principles electronic-structure calculations. It is shown that under compression stabilization or destabilization of the ground-state body-centered cubic (bcc) phase of the metal is mainly dictated by the band-structure energy that correlates well with the position of the Kohn anomaly in the transverse acoustic phonon mode. The predicted position of the Kohn anomaly in V, Nb, and Ta is found to be in a good agreement with data from the inelastic x-ray or neutron scattering measurements. In the case of alloying the change in phase stability is defined by the interplay between the band-structure and Madelung energies. We show that band-structure effects determine phase stability when a particular Group-VB metal is alloyed with its nearest neighbors within the same d-transition series: the neighbor with less and more d electrons destabilize and stabilize the bcc phase, respectively. When V is alloyed with neighbors of a higher (4d- or 5d-) transition series, both electrostatic Madelung and band-structure energies stabilize the body-centered-cubic phase. The opposite effect (destabilization) happens when Nb or Ta is alloyed with neighbors of the 3d-transition series.

  15. Precipitation of Niobium Boride Phases at the Base Metal/Weld Metal Interface in Dissimilar Weld Joints

    Science.gov (United States)

    Výrostková, Anna; Kepič, Ján; Homolová, Viera; Falat, Ladislav

    2015-07-01

    In this work, the analysis of failure mechanism in the heat affected zone is described in dissimilar weld joints between advanced martensitic steel T92 and Ni-base weld metal. The joints were treated with two different post-weld heat treatments and tested. For the creep, tensile, and Charpy impact tests, the samples with interfacially located notch were used. Moreover long term aging at 625 °C was applied before the tensile and notch toughness tests. Decohesion fractures ran along carbides at the T92 BM/WM interfaces in case of the modified PWHT, whereas type IV cracking was the prevailing failure mechanism after the classical PWHT in the creep test. In the notch tensile and Charpy impact tests, with the notch at T92 base metal/weld metal interface, fractures ran along the interface with a hard phase on the fracture surface along with the ductile dimple and brittle quasi-cleavage fracture. The phase identified as niobium boride (either NbB and/or Nb3B2) was produced during welding at the end of the solidification process. It was found in the welds regardless of the post-weld heat treatment and long-term aging.

  16. Earth Abundant Element Type I Clathrate Phases

    Directory of Open Access Journals (Sweden)

    Susan M. Kauzlarich

    2016-08-01

    Full Text Available Earth abundant element clathrate phases are of interest for a number of applications ranging from photovoltaics to thermoelectrics. Silicon-containing type I clathrate is a framework structure with the stoichiometry A8-xSi46 (A = guest atom such as alkali metal that can be tuned by alloying and doping with other elements. The type I clathrate framework can be described as being composed of two types of polyhedral cages made up of tetrahedrally coordinated Si: pentagonal dodecahedra with 20 atoms and tetrakaidecahedra with 24 atoms in the ratio of 2:6. The cation sites, A, are found in the center of each polyhedral cage. This review focuses on the newest discoveries in the group 13-silicon type I clathrate family: A8E8Si38 (A = alkali metal; E = Al, Ga and their properties. Possible approaches to new phases based on earth abundant elements and their potential applications will be discussed.

  17. Modelling of phase diagrams of nanoalloys with complex metallic phases: application to Ni-Sn.

    Science.gov (United States)

    Kroupa, A; Káňa, T; Buršík, J; Zemanová, A; Šob, M

    2015-11-14

    A method for modelling of size-dependent phase diagrams was developed by combining the semiempirical CALPHAD method and ab initio calculations of surface stresses for intermetallic phases. A novel approach was devised for the calculation of surface energy, free of systematic errors from the selection of different parameters of the software (e.g. number of the k-points) and for handling layered structures and off-stoichiometric slabs. Our approach allows the determination of complex size-dependent phase diagrams of systems with intermetallic phases, which was not possible up to now. The method was verified for the modelling of the phase diagram of the Ni-Sn system and basic comparison with rare experimental results was shown. There is reasonable agreement between the calculated and experimental results. The modelling of size-dependent phase diagrams of real systems allows the prediction of phase equilibria existing in nanosystems and possible changes in material properties. There is a need for such knowledge and the existence of reliable data for simpler systems is crucial for further application of this approach. This should motivate future experimental work.

  18. Phase engineering of monolayer transition-metal dichalcogenide through coupled electron doping and lattice deformation

    Energy Technology Data Exchange (ETDEWEB)

    Ouyang, Bin; Lan, Guoqiang; Song, Jun, E-mail: jun.song2@mcgill.ca [Department of Mining and Materials Engineering, McGill University, Montreal, Quebec H3A 0C5 (Canada); Guo, Yinsheng [Department of Chemistry, Columbia University, New York, New York 10027 (United States); Mi, Zetian [Department of Electrical and Computer Engineering, McGill University, Montreal, Quebec H3A 0E9 (Canada)

    2015-11-09

    First-principles calculations were performed to investigate the phase stability and transition within four monolayer transition-metal dichalcogenide (TMD) systems, i.e., MX{sub 2} (M = Mo or W and X = S or Se) under coupled electron doping and lattice deformation. With the lattice distortion and electron doping density treated as state variables, the energy surfaces of different phases were computed, and the diagrams of energetically preferred phases were constructed. These diagrams assess the competition between different phases and predict conditions of phase transitions for the TMDs considered. The interplay between lattice deformation and electron doping was identified as originating from the deformation induced band shifting and band bending. Based on our findings, a potential design strategy combining an efficient electrolytic gating and a lattice straining to achieve controllable phase engineering in TMD monolayers was demonstrated.

  19. Non-Fermi liquid phase in metallic Skyrmion crystals

    Science.gov (United States)

    Watanabe, Haruki; Parameswaran, Siddharth; Raghu, Srinivas; Vishwanath, Ashvin

    2014-03-01

    Motivated by reports of a non-Fermi liquid state in MnSi, we examine the effect of coupling phonons of an incommensurate skyrmion crystal (SkX) to conduction electrons. We find that non-Fermi liquid behavior emerges in both two and three dimensions over the entire phase, due to an anomalous electron-phonon coupling that is linked to the net skyrmion density. A small parameter, the spiral wave vector in lattice units, allows us to exercise analytic control and ignore Landau damping of phonons over a wide energy range. At the lowest energy scales the problem is similar to electrons coupled to a gauge field. The best prospects for realizing these effects is in short period skyrmion lattice systems such as MnGe or epitaxial MnSi films. We also compare our results with the unusual T 3 / 2 scaling of temperature dependent resistivity seen in high pressure experiments on MnSi. We acknowledge support from the NSF via Grant DMR-0645691, the DOE Office of Basic Energy Sciences via contract DE-AC02-76SF00515, and the Simons, Templeton, and Alfred P. Sloan Foundations.

  20. Surface effects and phase stability in metal oxides nanoparticles under visible irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Ricci, Pier Carlo, E-mail: carlo.ricci@dsf.unica.it; Carbonaro, C. M., E-mail: carlo.ricci@dsf.unica.it; Corpino, R., E-mail: carlo.ricci@dsf.unica.it; Chiriu, D., E-mail: carlo.ricci@dsf.unica.it; Stagi, L., E-mail: carlo.ricci@dsf.unica.it [Dipartimento di Fisica, Universitá degli Studi di Cagliari, S.P. Monserrato-Sestu Km 0,700, 09042 Monserrato (Canada) (Italy)

    2014-10-21

    The light induced phase transformation between stable phases of metal oxides nanoparticles is analyzed. The surrounding atmosphere as well as the defect density at the surface play a fundamental role. It has been found that in oxygen poor chamber atmosphere the phase transformation is favored, while the phase transition cannot be achieved if the defects at the surface are properly passivated. The phase transition is activated by intragap irradiation, able to activate the F- center at the surface connected to oxygen vacancies, and promoting the activation of the surface and the nucleation of neighboring crystallites. The phase transition was studied in Titanium oxide (TiO{sub 2}) and in Iron oxide (Fe{sub 2}O{sub 3}): Maghemite is subjected to a phase transformation to α−Fe{sub 2}O{sub 3} (hematite), Anatase nanoparticles converts to Rutile. The general mechanism of the phase transition and, more in general, the possibility to optically control the surface activity of metal oxides is discussed.

  1. Formation and Stability of High-Spin Alkali Clusters

    Science.gov (United States)

    Schulz, C. P.; Claas, P.; Schumacher, D.; Stienkemeier, F.

    2004-01-01

    Helium nanodroplet isolation has been applied to agglomerate alkali clusters at temperatures of 380mK. The very weak binding to the surface of the droplets allows a selection of only weakly bound, high-spin states. Here we show that larger clusters of alkali atoms in high-spin states can be formed. The lack of strong bonds from pairing electrons makes these systems nonmetallic, vanderWaals like complexes of metal atoms. We find that sodium and potassium readily form such clusters containing up to 25atoms. In contrast, this process is suppressed for rubidium and cesium. Apparently, for these heavy alkalis, larger high-spin aggregates are not stable and depolarize spontaneously upon cluster formation.

  2. Use of precalciners to remove alkali from raw materials in the cement industry. Final report, July 1978-July 1980

    Energy Technology Data Exchange (ETDEWEB)

    Gartner, E.M.

    1980-07-01

    The objective of this work was to develop an efficient means of removing alkali metal compounds (alkalies) from high-alkali aluminosilicate raw materials of the type commonly used as part of cement raw mixes in order to increase the energy efficiency of cement manufacture. The intention of this project was to determine whether the high-alkali raw materials could be pyroprocessed separately to remove the alkalies before they entered the rotary kiln, where they would be mixed with the other raw feed components. If this could be achieved, considerable savings could be made in the energy required to remove alkalies, compared to conventional methods in which the cement raw mix must be treated as a whole. Two different methods of alkali removal were examined, namely, vaporization of alkalies at relatively low temperatures; and alkali-rich melt separation at relativey high temperatures. The results showed that the removal of alkalies by pyroprocessing of high-alkali raw feed components separate from the other cement raw mix components is not likely to be a practical alternative to the best available conventional precalciner technology. (LCL)

  3. Generation of copper rich metallic phases from waste printed circuit boards.

    Science.gov (United States)

    Cayumil, R; Khanna, R; Ikram-Ul-Haq, M; Rajarao, R; Hill, A; Sahajwalla, V

    2014-10-01

    The rapid consumption and obsolescence of electronics have resulted in e-waste being one of the fastest growing waste streams worldwide. Printed circuit boards (PCBs) are among the most complex e-waste, containing significant quantities of hazardous and toxic materials leading to high levels of pollution if landfilled or processed inappropriately. However, PCBs are also an important resource of metals including copper, tin, lead and precious metals; their recycling is appealing especially as the concentration of these metals in PCBs is considerably higher than in their ores. This article is focused on a novel approach to recover copper rich phases from waste PCBs. Crushed PCBs were heat treated at 1150°C under argon gas flowing at 1L/min into a horizontal tube furnace. Samples were placed into an alumina crucible and positioned in the cold zone of the furnace for 5 min to avoid thermal shock, and then pushed into the hot zone, with specimens exposed to high temperatures for 10 and 20 min. After treatment, residues were pulled back to the cold zone and kept there for 5 min to avoid thermal cracking and re-oxidation. This process resulted in the generation of a metallic phase in the form of droplets and a carbonaceous residue. The metallic phase was formed of copper-rich red droplets and tin-rich white droplets along with the presence of several precious metals. The carbonaceous residue was found to consist of slag and ∼30% carbon. The process conditions led to the segregation of hazardous lead and tin clusters in the metallic phase. The heat treatment temperature was chosen to be above the melting point of copper; molten copper helped to concentrate metallic constituents and their separation from the carbonaceous residue and the slag. Inert atmosphere prevented the re-oxidation of metals and the loss of carbon in the gaseous fraction. Recycling e-waste is expected to lead to enhanced metal recovery, conserving natural resources and providing an environmentally

  4. The basic research on the CDA initiation phase for a metallic fuel FBR

    Energy Technology Data Exchange (ETDEWEB)

    Hirano, Go; Hirakawa, Naohiro [Tohoku Univ., Sendai (Japan); Kawada, Ken-ichi; Niwa, Hazime

    1998-03-01

    A metallic fuel with novel design has received great deal of interest recently as an option of advanced fuel to be substituted MOX fuel, however, the behavior at the transient has not been studied in many aspects. Therefore, for the purpose to show the basic tendency of the behavior and released energy at CDA (core disruptive accident) for a metallic fuel FBR and to prepare the basic knowledge for consideration of the adoption of the advanced fuel, Tohoku University and Power Reactor and Nuclear Fuel Development Corporation have made a joint research entitled. (1) Target and Results of analysis: The accident initiator considered is a LOF accident with ATWS. The LOF analysis was performed for a metallic fuel 600 MWe homogeneous two region core at the beginning of cycle, both for an ordinary metallic fuel core and for a metallic fuel core with ZrH pins. It was necessary mainly to change the constants of input parameters to apply the code for the analysis of a metallic fueled reactor. These changes were made by assuming appropriate models. Basic LOF cases and all blackout case that assumed using electromagnetic pumps were analyzed. The results show that the basic LOF cases for a metallic fuel core and all the cases for a metallic fuel core with ZrH pins could be avoided to become prompt-critical, and mildly transfer to the transient phase. (2) Improvement of CDA initiation phase analysis code: At present, it is difficult for the code to adapt to the large material movement to in the core at the transient. Therefore, the nuclear calculation model in the code was improved by using the adiabatic space dependent kinetics. The results of a sample case, that is a metallic fueled core at the beginning of cycle, show this improvement is appropriate. (3) Conclusion: The behavior at CDA of a metallic fueled core of a fast reactor was analyzed using the CDA initiation phase analysis code and the knowledge of the important characteristics at the CDA initiation phase was obtained

  5. Why do disk galaxies present a common gas-phase metallicity gradient?

    Science.gov (United States)

    Chang, R.; Zhang, Shuhui; Shen, Shiyin; Yin, Jun; Hou, Jinliang

    2017-03-01

    CALIFA data show that isolated disk galaxies present a common gas-phase metallicity gradient, with a characteristic slope of -0.1dex/re between 0.3 and 2 disk effective radius re (Sanchez et al. 2014). Here we construct a simple model to investigate which processes regulate the formation and evolution.

  6. Utilization of Mineral Wools as Alkali-Activated Material Precursor

    Directory of Open Access Journals (Sweden)

    Juho Yliniemi

    2016-04-01

    Full Text Available Mineral wools are the most common insulation materials in buildings worldwide. However, mineral wool waste is often considered unrecyclable because of its fibrous nature and low density. In this paper, rock wool (RW and glass wool (GW were studied as alkali-activated material precursors without any additional co-binders. Both mineral wools were pulverized by a vibratory disc mill in order to remove the fibrous nature of the material. The pulverized mineral wools were then alkali-activated with a sodium aluminate solution. Compressive strengths of up to 30.0 MPa and 48.7 MPa were measured for RW and GW, respectively, with high flexural strengths measured for both (20.1 MPa for RW and 13.2 MPa for GW. The resulting alkali-activated matrix was a composite-type in which partly-dissolved fibers were dispersed. In addition to the amorphous material, sodium aluminate silicate hydroxide hydrate and magnesium aluminum hydroxide carbonate phases were identified in the alkali-activated RW samples. The only crystalline phase in the GW samples was sodium aluminum silicate. The results of this study show that mineral wool is a very promising raw material for alkali activation.

  7. Homochiral metal-organic framework used as a stationary phase for high-performance liquid chromatography.

    Science.gov (United States)

    Kong, Jiao; Zhang, Mei; Duan, Ai-Hong; Zhang, Jun-Hui; Yang, Rui; Yuan, Li-Ming

    2015-02-01

    Metal-organic frameworks are promising porous materials. Chiral metal-organic frameworks have attracted considerable attention in controlling enantioselectivity. In this study, a homochiral metal-organic framework [Co(2) (D-cam)(2) (TMDPy)] (D-cam = D-camphorates, TMDPy = 4,4'-trimethylenedipyridine) with a non-interpenetrating primitive cubic net has been used as a chiral stationary phase in high-performance liquid chromatography. It has allowed the successful separation of six positional isomers and six chiral compounds. The good selectivity and baseline separation, or at least 60% valley separation, confirmed its excellent molecular recognition characteristics. The relative standard deviations for the retention time of run-to-run and column-to-column were less than 1.8 and 3.1%, respectively. These results demonstrate that [Co(2) (D-cam)(2) (TMDPy)] may represent a promising chiral stationary phase for use in high-performance liquid chromatography.

  8. Polarization conversion based on plasmonic phase control by an ultra-thin metallic nano-strips

    Science.gov (United States)

    Wei, Helei; Hu, Dejiao; Deng, Yunsheng; Wu, Xuannan; Xiao, Xiao; Hou, Yidong; Wang, Yunjiao; Shi, Ruiying; Wang, Deqiang; Du, Jinglei

    2016-12-01

    Ultra-thin metallic nano-strips (thinner than skin depth) can lead to anomalous reflection for a transverse magnetic (TM) incidence of some wave-lengths, due to the phase modulation of localized surface plasmon resonance. Based on the principle above, we proposed a method of polarization modulation using ultra-thin metallic nano-strips. When irradiating nano-strips vertically by light with a given polarized angle, we can utilize the phase difference of the TM transmission and transverse electric (TE) transmission near anomalous reflection region to modulate transmission polarization. We have designed and fabricated the ultra-thin metallic nano-strips with the function of quarter-wave plate, the attained transmission Stokes parameter S3 is 0.95. The nano-strips is easy to design and fabricate, also compatible with other optics devices, hence has the potential applications in integrated optics field.

  9. Damage detection in multilayered fiber-metal laminates using guided-wave phased array

    Energy Technology Data Exchange (ETDEWEB)

    Maghsoodi, Ameneh; Ohadi, Abdolrezap; Sadighi, Mojtaba; Amindavar, Hamidreza [Amirkabir University, Tehran (Iran, Islamic Republic of)

    2016-05-15

    This study employs the Lamb wave method to detect damage in Fiber-metal laminates (FMLs). The method is based on quasiisotropic behavior approximation and beam forming techniques. Delay and sum and minimum variance distorsionless response beam formers are applied to a uniform linear phased array. The simulation in finite element software is conducted to evaluate the performance of the presented procedure. The two types of damage studied are the following: (1) Delamination between fiber-epoxy and metal layers and (2) crack on the metal layer. The present study has the following important contributions: (1) Health monitoring of multi-damaged FMLs using Lamb waves and beam forming technique, (2) detection of damage type, (3) detection of damage size by 1D phased array, and (4) identification of damages that occurred very close to the laminate edges or close to each other.

  10. Predicted novel metallic metastable phases of polymeric nitrogen at high pressures

    Science.gov (United States)

    Wang, Xiaoli; Tian, Fubo; Wang, Lin; Jin, Xilian; Duan, Defang; Huang, Xiaoli; Liu, Bingbing; Cui, Tian

    2013-01-01

    Two new metallic polymeric structures of nitrogen, Pnnm and Cccm, are found by means of the first-principles density functional theory and a random structure-searching method. Firstly, it is shown that the transition behavior of nitrogen from insulator to metal starts at a pressure of approximately 460 GPa at 0 K. The Pnnm phase becomes energetically favorable with respect to cubic gauche at 363 GPa, and then transforms to the Cccm structure at 884 GPa. Electron-phonon coupling calculations suggest that the Pnnm crystal possesses superconductivity. The stability of these two phases is also explored, showing for the first time that they are stable structures of nitrogen exhibiting metallic properties.

  11. High-internal-phase emulsions stabilized by metal-organic frameworks and derivation of ultralight metal-organic aerogels

    Science.gov (United States)

    Zhang, Bingxing; Zhang, Jianling; Liu, Chengcheng; Peng, Li; Sang, Xinxin; Han, Buxing; Ma, Xue; Luo, Tian; Tan, Xiuniang; Yang, Guanying

    2016-01-01

    To design high-internal-phase emulsion (HIPE) systems is of great interest from the viewpoints of both fundamental researches and practical applications. Here we demonstrate for the first time the utilization of metal-organic framework (MOF) for HIPE formation. By stirring the mixture of water, oil and MOF at room temperature, the HIPE stabilized by the assembly of MOF nanocrystals at oil-water interface could be formed. The MOF-stabilized HIPE provides a novel route to produce highly porous metal-organic aerogel (MOA) monolith. After removing the liquids from the MOF-stabilized HIPE, the ultralight MOA with density as low as 0.01 g·cm−3 was obtained. The HIPE approach for MOA formation has unique advantages and is versatile in producing different kinds of ultralight MOAs with tunable porosities and structures. PMID:26892258

  12. A quantum phase transition between a topological and a trivial semi-metal in holography

    CERN Document Server

    Landsteiner, Karl; Sun, Ya-Wen

    2015-01-01

    We present a holographic model of a topological Weyl semi-metal state. Key ingredient is a time-reversal breaking parameter and a mass deformation. Upon varying the ratio of mass to time reversal breaking parameter the model undergoes a quantum phase transition from a topologically non-trivial state to a trivial one. The order parameter for this phase transition is the anomalous Hall effect (AHE). The results can be interpreted in terms of the holographic RG flow leading to restoration of time reversal at the end point of the RG flow in the trivial phase.

  13. Phase measurements of erythrocytes affected by metal ions with quantitative interferometric microscopy

    Science.gov (United States)

    Wang, Shouyu; Yan, Keding; Shan, Yanke; Xu, Mingfei; Liu, Fei; Xue, Liang

    2015-12-01

    Erythrocyte morphology is an important factor in disease diagnosis, however, traditional setups as microscopes and cytometers cannot provide enough quantitative information of cellular morphology for in-depth statistics and analysis. In order to capture variations of erythrocytes affected by metal ions, quantitative interferometric microscopy (QIM) is applied to monitor their morphology changes. Combined with phase retrieval and cell recognition, erythrocyte phase images, as well as phase area and volume, can be accurately and automatically obtained. The research proves that QIM is an effective tool in cellular observation and measurement.

  14. Exploring Systematic Effects in the Relation Between Stellar Mass, Gas Phase Metallicity, and Star Formation Rate

    CERN Document Server

    Telford, O Grace; Skillman, Evan D; Conroy, Charlie

    2016-01-01

    There is evidence that the well-established mass-metallicity relation in galaxies is correlated with a third parameter: star formation rate (SFR). The strength of this correlation may be used to disentangle the relative importance of different physical processes (e.g., infall of pristine gas, metal-enriched outflows) in governing chemical evolution. However, all three parameters are susceptible to biases that might affect the observed strength of the relation between them. We analyze possible sources of systematic error, including sample bias, application of S/N cuts on emission lines, choice of metallicity calibration, uncertainty in stellar mass determination, aperture effects, and dust. We present the first analysis of the relation between stellar mass, gas phase metallicity, and SFR using strong line abundance diagnostics from Dopita et al. (2013) for ~130,000 star-forming galaxies in the Sloan Digital Sky Survey and provide a detailed comparison of these diagnostics in an appendix. Using these abundance ...

  15. Interface Characterization of Metals and Metal-nitrides to Phase Change Materials

    NARCIS (Netherlands)

    Roy, Deepu; Wolters, Rob A.M.

    2011-01-01

    We have investigated the interfacial contact properties of the CMOS compatible electrode materials W, TiW, Ta, TaN and TiN to doped-Sb2Te phase change material (PCM). This interface is characterized both in the amorphous and in the crystalline state of the doped-Sb2Te. The electrical nature of the i

  16. Why do high-redshift galaxies show diverse gas-phase metallicity gradients?

    Science.gov (United States)

    Ma, Xiangcheng; Hopkins, Philip F.; Feldmann, Robert; Torrey, Paul; Faucher-Giguère, Claude-André; Kereš, Dušan

    2017-01-01

    Recent spatially resolved observations of galaxies at z ˜ 0.6-3 reveal that high-redshift galaxies show complex kinematics and a broad distribution of gas-phase metallicity gradients. To understand these results, we use a suite of high-resolution cosmological zoom-in simulations from the Feedback in Realistic Environments (FIRE) project, which include physically motivated models of the multi-phase ISM, star formation, and stellar feedback. Our simulations reproduce the observed diversity of kinematic properties and metallicity gradients, broadly consistent with observations at z ˜ 0-3. Strong negative metallicity gradients only appear in galaxies with a rotating disk, but not all rotationally supported galaxies have significant gradients. Strongly perturbed galaxies with little rotation always have flat gradients. The kinematic properties and metallicity gradient of a high-redshift galaxy can vary significantly on short time-scales, associated with starburst episodes. Feedback from a starburst can destroy the gas disk, drive strong outflows, and flatten a pre-existing negative metallicity gradient. The time variability of a single galaxy is statistically similar to the entire simulated sample, indicating that the observed metallicity gradients in high-redshift galaxies reflect the instantaneous state of the galaxy rather than the accretion and growth history on cosmological time-scales. We find weak dependence of metallicity gradient on stellar mass and specific star formation rate (sSFR). Low-mass galaxies and galaxies with high sSFR tend to have flat gradients, likely due to the fact that feedback is more efficient in these galaxies. We argue that it is important to resolve feedback on small scales in order to produce the diverse metallicity gradients observed.

  17. Phase transition and possible metallization in CeVO{sub 4} under pressure

    Energy Technology Data Exchange (ETDEWEB)

    Garg, Alka B., E-mail: alkagarg@barc.gov.in [High Pressure and Synchrotron Radiation Physics Division, Bhabha Atomic Research Centre, Mumbai 400085, Maharashtra (India); Shanavas, K.V. [High Pressure and Synchrotron Radiation Physics Division, Bhabha Atomic Research Centre, Mumbai 400085, Maharashtra (India); Wani, B.N. [Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400085, Maharashtra (India); Sharma, Surinder M. [High Pressure and Synchrotron Radiation Physics Division, Bhabha Atomic Research Centre, Mumbai 400085, Maharashtra (India)

    2013-07-15

    Phase stability of CeVO{sub 4} under pressure has been investigated using synchrotron based angle dispersive x-ray diffraction (ADXRD), electrical resistance and first principles calculations. The results indicate that the ambient zircon structure of the compound transforms to a low symmetry monoclinic monazite phase beyond 3.8 GPa with nearly 8.6% volume discontinuity. Beyond 11 GPa, the pattern could be fitted to a similar monazite structure which is about 12.7% denser and has a much larger monoclinic beta angle. On pressure release the first monoclinic phase is recovered. The electrical resistance data show a large drop in resistance with pressure indicating substantial narrowing down of the band gap. Electronic structure calculations support these observations and suggest possible pressure induced metallization in this material. - Pressure induced structural phase transition in CeVO{sub 4} as observed by x- ray diffraction (pressure vs. volume) and possible metallization in CeVO{sub 4} through electrical resistance and first principles electronic structure calculations. - Highlights: • Structural and electrical behavior of CeVO{sub 4} under pressure studied using x-ray diffraction and electrical resistance measurements and first principles calculations. • Two successive structural transitions confirmed by experiment and theory: zircon–monazite I–monazite II. • Band gap collapse and possible metallization is indicated by electrical resistance measurements and electronic structure calculations under pressure. • Novel observation of lower bulk modulus in the high pressure phase (both by experiment and calculations) explained through structural analysis.

  18. Development of Detection Method for Chlorates of Alkali Metals in Cosmetics%化妆品中碱金属氯酸盐的检测方法研究

    Institute of Scientific and Technical Information of China (English)

    杨轶眉; 李勤; 薛峰

    2014-01-01

    A thin layer chromatography(TCL)&potentiometric titration method was developed for the determination of chlo-rates of alkali metals in cosmetics. Chlorates were separated from other halates by thin layer chromatography and identified by the oxidation of iodide to form iodine. After identification,chlorate was reduced by zinc powder under acid conditions. The formed chloride was measured by potentiometric titration using a silver nitrate solution. The results showed that the recovery of the method was in the range of 81.4% to 105.2% under the concentration of 0.03% to 3.41% while being counted as chlorate ions(with relative standard deviation of not more than 10% ). Additionally,the detection and quantification limits were found to be 0.03% and 0.10% respectively.%建立了薄层色谱法和电位滴定法联用测定化妆品中碱金属氯酸盐含量的方法。用薄层色谱将氯酸盐从其他卤酸盐中分离,与碘化物形成碘来鉴别碱金属的氯酸盐。通过鉴别试验后,在酸性条件下氯酸盐被锌粉还原,所形成的氯化物用硝酸银溶液进行电位滴定。试验结果表明:在0.03%~3.41%(以氯酸根离子计)的质量分数范围内,加标回收率为81.4%~105.2%,相对标准偏差(RSD)≤10%;定性检出限为0.03%(质量分数),定量检出限为0.10%(质量分数)。

  19. Alkali-metal ion coordination in uranyl(VI) poly-peroxide complexes in solution. Part 1: the Li⁺, Na⁺ and K⁺--peroxide-hydroxide systems.

    Science.gov (United States)

    Zanonato, Pier Luigi; Di Bernardo, Plinio; Vallet, Valerie; Szabó, Zoltán; Grenthe, Ingmar

    2015-01-28

    The alkali metal ions Li(+), Na(+) and K(+) have a profound influence on the stoichiometry of the complexes formed in uranyl(VI)-peroxide-hydroxide systems, presumably as a result of a templating effect, resulting in the formation of two complexes, M[(UO2)(O2)(OH)]2(-) where the uranyl units are linked by one peroxide bridge, μ-η(2)-η(2), with the second peroxide coordinated "end-on", η(2), to one of the uranyl groups, and M[(UO2)(O2)(OH)]4(3-), with a four-membered ring of uranyl ions linked by μ-η(2)-η(2) peroxide bridges. The stoichiometry and equilibrium constants for the reactions: M(+) + 2UO2(2+) + 2HO2(-) + 2H2O → M[(UO2)(O2)(OH)]2(-) + 4H(+) (1) and M(+) + 4UO2(2+) + 4HO2(-) + 4H2O → M[(UO2)(O2)(OH)]4(3-) + 8H(+) (2) have been measured at 25 °C in 0.10 M (tetramethyl ammonium/M(+))NO3 ionic media using reaction calorimetry. Both reactions are strongly enthalpy driven with large negative entropies of reaction; the observation that ΔH(2) ≈ 2ΔH(1) suggests that the enthalpy of reaction is approximately the same when peroxide is added in bridging and "end-on" positions. The thermodynamic driving force in the reactions is the formation of strong peroxide bridges and the role of M(+) cations is to provide a pathway with a low activation barrier between the reactants and in this way "guide" them to form peroxide bridged complexes; they play a similar role as in the synthesis of crown-ethers. Quantum chemical (QC) methods were used to determine the structure of the complexes, and to demonstrate how the size of the M(+)-ions affects their coordination geometry. There are several isomers of Na[(UO2)(O2)(OH)]2(-) and QC energy calculations show that the ones with a peroxide bridge are substantially more stable than the ones with hydroxide bridges. There are isomers with different coordination sites for Na(+) and the one with coordination to the peroxide bridge and two uranyl oxygen atoms is the most stable one.

  20. Electronic Structure and Spin Configuration Trends of Single Transition Metal Impurity in Phase Change Material

    Science.gov (United States)

    Li, H.; Pei, J.; Shi, L. P.

    2016-10-01

    Fe doped phase change material GexSbyTez has shown experimentally the ability to alter its magnetic properties by phase change. This engineered spin degree of freedom into the phase change material offers the possibility of logic devices or spintronic devices where they may enable fast manipulation of ferromagnetism by a phase change mechanism. The electronic structures and spin configurations of isolated transition metal dopant in phase change material (iTM-PCM) is important to understand the interaction between localized metal d states and the unique delocalized host states of phase change material. Identifying an impurity center that has, in isolation, a nonvanishing magnetic moment is the first step to study the collective magnetic ordering, which originates from the interaction among close enough individual impurities. Theoretical description of iTM-PCM is challenging. In this work, we use a screened exchange hybrid functional to study the single 3d transition metal impurity in crystalline GeTe and GeSb2Te4. By curing the problem of local density functional (LDA) such as over-delocalization of the 3d states, we find that Fe on the Ge/Sb site has its majority d states fully occupied while its minority d states are empty, which is different from the previously predicted electronic configuration by LDA. From early transition metal Cr to heavier Ni, the majority 3d states are gradually populated until fully occupied and then the minority 3d states begin to be filled. Interpretive orbital interaction pictures are presented for understanding the local and total magnetic moments.

  1. Association of soil organic matter with metal phases examined by selective dissolution approach: limitations and advantages

    Science.gov (United States)

    Wagai, R.; Mayer, L. M.

    2014-12-01

    Positive co-variation of organic matter (OM) with iron and aluminum phases has been known for decades in soil and, in case of OM-Fe, in marine sediments. More recent studies point to the metal control on the mean residence time of organic carbon in soils, suggesting that better understanding of the role of these metal phases and the nature of these organo-metal associations would help to improve the models of soil OM dynamics. We developed a selective dissolution approach to assess these associations (Wagai and Mayer, 2007; Wagai et al., 2013). By taking advantage of well-established extraction techniques that were targeted to dissolve specific metal and aluminosilicate phases in soil, we quantified the amounts of OM co-dissolved by the selective dissolution of these inorganic phases. The inherent limitations in this conceptually simple approach include the presence of C-based compounds (often as complexing agent for metal) in the extractants and the lack of selectivity when dissolving specific inorganic phases. The former was resolved by using nitrogen (N), instead of C, as a surrogate for OM because (i) soil N is mostly present as soil OM with relatively narrow C:N ratio, and (ii) the extractants are N free. We were able to partially overcome the lack of selectivity problem by comparing the co-dissolution of OM from a variety of extractants that use reductive, complexation, and acid/alkaline dissolutions. The potential advantages of our approach include the ability (i) to estimate the contribution of specific inorganic phases to OM stabilization, and (ii) to infer the possible modes of the organo-mineral associations that were extracted from field soils (e.g., adsorptive association vs. coprecipitation of organo-metallic complexes). In this presentation, we will further consider the advantages and limitations of this approach (e.g., methodological cautions), present some of the previous and new findings gained from this approach (including its application to

  2. Positron collisions with alkali-metal atoms

    Science.gov (United States)

    Gien, T. T.

    1990-01-01

    The total cross sections for positron and electron collisions with potassium, sodium, lithium and rubidium are calculated, employing the modified Glauber approximation. The Modified Glauber cross sections for positron collision with potassium and sodium at low intermediate energies are found to agree reasonably well with existing experimental data.

  3. Study on the melting process of phase change materials in metal foams using lattice Boltzmann method

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    A thermal lattice Boltzmann model is developed for the melting process of phase change material (PCM) embedded in open-cell metal foams. Natural convection in the melt PCM is considered. Under the condition of local thermal non-equilibrium between the metal matrix and PCM, two evolution equations of temperature distribution function are pre-sented through selecting an equilibrium distribution function and a nonlinear source term properly. The enthalpy-based method is employed to copy with phase change problem. Melting process in a cavity of the metal foams is simulated using the present model. The melting front locations and the temperature distributions in the metal foams filled with PCM are obtained by the lattice Boltzmann method. The effects of the porosity and pore size on the melting are also investigated and discussed. The re-sults indicate that the effects of foam porosity play important roles in the overall heat transfer. For the lower porosity foams, the melting rate is comparatively greater than the higher porosity foams, due to greater heat conduction from metal foam with high heat conductivity. The foam pore size has a limited effect on the melting rate due to two counteracting effects between conduction and convection heat transfer.

  4. Non-Fermi-liquid d-wave metal phase of strongly interacting electrons.

    Science.gov (United States)

    Jiang, Hong-Chen; Block, Matthew S; Mishmash, Ryan V; Garrison, James R; Sheng, D N; Motrunich, Olexei I; Fisher, Matthew P A

    2013-01-03

    Developing a theoretical framework for conducting electronic fluids qualitatively distinct from those described by Landau's Fermi-liquid theory is of central importance to many outstanding problems in condensed matter physics. One such problem is that, above the transition temperature and near optimal doping, high-transition-temperature copper-oxide superconductors exhibit 'strange metal' behaviour that is inconsistent with being a traditional Landau Fermi liquid. Indeed, a microscopic theory of a strange-metal quantum phase could shed new light on the interesting low-temperature behaviour in the pseudogap regime and on the d-wave superconductor itself. Here we present a theory for a specific example of a strange metal--the 'd-wave metal'. Using variational wavefunctions, gauge theoretic arguments, and ultimately large-scale density matrix renormalization group calculations, we show that this remarkable quantum phase is the ground state of a reasonable microscopic Hamiltonian--the usual t-J model with electron kinetic energy t and two-spin exchange J supplemented with a frustrated electron 'ring-exchange' term, which we here examine extensively on the square lattice two-leg ladder. These findings constitute an explicit theoretical example of a genuine non-Fermi-liquid metal existing as the ground state of a realistic model.

  5. Mineral phases containing heavy metals in the suspended dust from Budapest, Hungary

    Directory of Open Access Journals (Sweden)

    Sipos P.

    2013-04-01

    Full Text Available The mineralogy, geochemistry and magnetic properties of total suspended particulate (TSP matter in Budapest, Hungary were studied to identify their heavy metal-bearing mineral phases. Amorphous organic matter, magnetite, salts as well as mineral phases characteristic of the surrounding geology are the main components of the TSP. They show significant enrichment in several heavy metals, such as Zn (up to 19 046 mg/kg, Pb (up to 3597 mg/kg, Cu (up to 699 mg/kg and Mo (up to 53 mg/kg. The most frequent heavy metal-bearing mineral phases are spherular or xenomorphic magnetite particles containing 2-3 wt% Pb and Zn. They often form aggregates and are closely associated with soot and/or clay minerals. The size of these particles is rarely below 30 nm. Cu and Mo could be associated to magnetite too. Clay minerals and mica particles may also contain significant amount of Zn (up to 5wt%. Additionally, ZnO and ZnCO3 particles were found in the sample with highest Zn content and our data suggest the potential association of Pb and carbonates, as well. Magnetite particles are resistant to weathering releasing its toxic components slowly to the environment, while layer silicates (and carbonates may be the potential source of mobile toxic metals in the TSP.

  6. IR spectroscopy of cationized aliphatic amino acids: Stability of charge-solvated structure increases with metal cation size

    NARCIS (Netherlands)

    Drayss, M. K.; Armentrout, P. B.; Oomens, J.; Schaefer, M.

    2010-01-01

    Gas-phase structures of alkali metal cationized (Li+, Na+,K+, Rb+, and Cs+) proline (Pro) and N-methyl alanine have been investigated using infrared multiple photon dissociation (IRMPD) spectroscopy utilizing light generated by a free electron laser and computational modeling. Measured IRMPD spectra

  7. IR spectroscopy of cationized aliphatic amino acids: Stability of charge-solvated structure increases with metal cation size

    NARCIS (Netherlands)

    Drayß, M.K.; Armentrout, P.B.; Oomens, J.; Schäfer, M.

    2010-01-01

    Gas-phase structures of alkali metal cationized (Li+, Na+, K+, Rb+, and Cs+) proline (Pro) and N-methyl alanine have been investigated using infrared multiple photon dissociation (IRMPD) spectroscopy utilizing light generated by a free electron laser and computational modeling. Measured IRMPD spectr

  8. Liquid phase micro-extraction: Towards the green methodology for ultratrace metals determination in aquatic ecosystems

    Directory of Open Access Journals (Sweden)

    López-López J. A.

    2013-04-01

    Full Text Available Heavy metals are normally found, in natural waters, in very low concentrations. Some of them are essential for life in low level; however, in higher level they are toxic. Therefore, analyzing their bio-available fraction is of main interest. Standard methodology is based in the collection of a number of samples from a water body. Collected samples must be stored, pre-treated and then analyzed. Pre-treatment usually involves pre-concentrating the metal, with the corresponding risk of contamination or loss of analyte. This way, punctual information is obtained from every sampling campaign. As an alternative, passive sampling techniques allow the continuous and coupled sampling-pre-treatment for heavy metals analysis, giving a better approach in the characterization of the studied water body. Liquid phase micro-extraction (LPME is a green analytical alternative for liquid-liquid extraction that promotes a reduction of sample volume, solvent needed and waste generation. Using these systems, polypropylene hollow fibers (HF with pores in their walls can be used. A few micro-liters of organic solvent are supported in the pores. The sample is placed in the outer part of the fiber and a receiving phase is placed in its inner part, allowing continuous liquid extraction of the metal from the sample. Several fibers with different physical features have been employed to analyzed total concentration and bio-availability of some heavy metals (Ag, Ni, Cu in natural water samples. Thanks to fibers configuration, devices for passive sampling based in HF-LPME could be designed. Advantages of this methodology over existing ones are supported because the receiving phase is liquid. As a consequence, retained metals do not need to be eluted from the acceptor prior to instrumental analysis.

  9. A New Process for Hot Metal Production at Low Fuel Rate - Phase 1 Feasibility Study

    Energy Technology Data Exchange (ETDEWEB)

    Dr. Wei-Kao Lu

    2006-02-01

    The project is part of the continuing effort by the North American steel industry to develop a coal-based, cokeless process for hot metal production. The objective of Phase 1 is to determine the feasibility of designing and constructing a pilot scale facility with the capacity of 42,000 mtpy of direct reduced iron (DRI) with 95% metallization. The primary effort is performed by Bricmont, Inc., an international engineering firm, under the supervision of McMaster University. The study focused on the Paired Straight Hearth furnace concept developed previously by McMaster University, The American Iron and Steel Institute and the US Department of Energy.

  10. The Measuring Method of Atomic Polarization of Alkali Metal Vapor Based on Optical Rotation and the Analysis of the Influence Factors%基于光偏振旋转效应的碱金属气室原子极化率测量方法及影响因素分析

    Institute of Scientific and Technical Information of China (English)

    尚慧宁; 全伟; 陈瑶; 李洋; 李红

    2016-01-01

    利用原子自旋效应能够实现超高灵敏度的惯性和磁场测量.一类操控原子自旋处于无自旋交换弛豫态的器件可以进行物理参数测量.碱金属气室为该类器件的敏感表头.碱金属原子密度与原子极化率是碱金属气室的重要参数 ,对研究原子自旋处于无自旋交换弛豫态有着重要的作用.光的偏振效应在量子计算和原子物理研究中发挥了重要作用.利用光的偏振效应能够实现对碱金属原子密度与原子极化率的检测.提出一种基于光偏振旋转效应的碱金属原子极化率测量方法.首先对碱金属气室加恒定磁场 ,利用激光作为检测光 ,根据光偏振旋转原理 ,检测通过气室的偏振光的法拉第旋转角 ,得到碱金属气室原子密度.然后将碱金属原子抽运 ,利用激光作为检测光 ,检测通过气室的偏振光的偏转角 ,得到碱金属原子极化率.该方法在测量原子极化率的过程中也测量了碱金属原子密度 ,实现利用一套系统测量两个重要参数 ,具有快速测量和高灵敏度等特点 ,简化了实验设备及过程.对两种偏转角进行仿真分析 ,得到该方法实验时检测激光波长变化对偏转角的影响 ,根据仿真图得到检测激光波长的可取范围 ,验证了该方法的可行性.最后分析激光器波长波动与磁场波动对其测量精度的影响 ,提出实验对激光器与磁场的要求.%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-ex-change-relaxation-free regime .Besides

  11. Production of Decorative Cast Metal Matrix Composites with a Complex Relief and Nonmetal Reinforcement Phase

    Directory of Open Access Journals (Sweden)

    Daniela Spasova

    2016-02-01

    Full Text Available The present paper is relevant to the research of possibilities for the production of decorative complex relief metal matrix composites (MMCs of the “invitro” type, with unformed and unchanging reinforcement (strengthening phase in the process of creating a composite. The research on the methods of metal matrix composites development in this paper has been brought to the application of different space vacuum schemes for composite synthesisof vacuuming the space for composites synthesis by using the notion of the “capillary forming”. In this method the metal matrix (copper alloy melt was infiltrated in the space between the pellets of reinforcement phase (quartz particles – SiO2, whereas the classical method adopted for the obtaining MMCs “in vitro”, uses a mechanism of forced insertion of the reinforcement phase into the ready for use melt, followed by homogenization of the composite structure. In the particular case, because the obtained composite will have a complex relief three-dimensional surface, the conditions for compacting the building phases in the three directions x, y, z should be virtually equalized. In order to accomplish the task set, a laboratory system is developed. The experiments were conducted with laboratory equipment elaborated on the base of another equipment for "capillary forming" with extra vacuum. The structures of the obtained MMCs were tested by metallographic analysis.

  12. A Transition to Metallic Hydrogen: Evidence of the Plasma Phase Transition

    Science.gov (United States)

    Silvera, Isaac; Zaghoo, Mohamed; Salamat, Ashkan

    The insulator-metal transition in hydrogen is one of the most outstanding problems in condensed matter physics. The high-pressure metallic phase is now predicted to be liquid atomic from T =0 K to very high temperatures. We have conducted measurements of optical properties of hot dense hydrogen in the region of 1.1-1.7 Mbar and up to 2200 K in a diamond anvil cell using pulsed laser heating of the sample. We present evidence in two forms: a plateau in the heating curves (average laser power vs temperature) characteristic of a first-order phase transition with latent heat, and changes in transmittance and reflectance characteristic of a metal for temperatures above the plateau temperature. For thick films the reflectance saturates at ~0.5. The phase line of this transition has a negative slope in agreement with theories of the so-called plasma phase transition. The NSF, Grant DMR-1308641, the DOE Stockpile Stewardship Academic Alliance Program, Grant DE-FG52-10NA29656, and NASA Earth and Space Science Fellowship Program, Award NNX14AP17H supported this research.

  13. Effects of alkali metals on catalyst of MnOx-CeO2/ZrO2-PILC in the low-temperature selective catalytic reduction%碱土金属对MnOx-CeO2/ZrO2-PILC催化剂SCR活性影响研究

    Institute of Scientific and Technical Information of China (English)

    沈伯雄; 陈建宏; 姚燕; 胡国丽

    2012-01-01

    The poisoning effects of alkali metals on low-temperature selective catalytic reduction (SCR) catalyst MnOx-CeO2/ZrO2-PILC were invested by the method of impregnation in the laboratory. It was indicated that the addition of Ca/Mg would decrease the activities of the catalyst, and the poisoning effects were contacted with the amount and acidity of the doped-alkali metal. X-ray diffraction (XRD) , H2-temperature programmed reduction (H2-TPR) , N2 adsorption-desorption and temperature-programmed desorption of NH3(NH3-TPD) were used to characterize the properties of the fresh and alkali earth doped catalysts. According to the results, the doped-alkali metals would inhibit the reduction properties, induce the loss in surface area and surface acidity.%采用浸渍法模拟低温选择性催化还原(SCR)催化剂MnOx-CeO2/ZrO2-PILC的碱土金属中毒特性,研究了碱土金属及其负载量对中毒程度的影响.实验表明,钙/镁的添加会引起催化剂中毒,催化剂中毒失活程度与碱土金属的负载量有关.运用X射线衍射(XRD)、H2程序升温还原(H2-TPR)、氮气吸脱附及NH3程序升温脱附(NH3-TPD)对新鲜催化剂以及碱土金属中毒后的催化剂进行了表征.结果表明,钙/镁中毒后催化剂的比表面积降低、催化剂氧化还原性和表面酸性减少,进而造成催化剂失活.

  14. In situ alkali-silica reaction observed by x-ray microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Kurtis, K.E.; Monteiro, P.J.M. [Univ. of California, Berkeley, CA (United States); Brown, J.T.; Meyer-Ilse, W. [Ernest Orlando Lawrence Berkeley National Lab., CA (United States)

    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.

  15. Liquid-phase extraction coupled with metal-organic frameworks-based dispersive solid phase extraction of herbicides in peanuts.

    Science.gov (United States)

    Li, Na; Wang, Zhibing; Zhang, Liyuan; Nian, Li; Lei, Lei; Yang, Xiao; Zhang, Hanqi; Yu, Aimin

    2014-10-01

    Liquid-phase extraction coupled with metal-organic frameworks-based dispersive solid phase extraction was developed and applied to the extraction of pesticides in high fatty matrices. The herbicides were ultrasonically extracted from peanut using ethyl acetate as extraction solvent. The separation of the analytes from a large amount of co-extractive fat was achieved by dispersive solid-phase extraction using MIL-101(Cr) as sorbent. In this step, the analytes were adsorbed on MIL-101(Cr) and the fat remained in bulk. The herbicides were separated and determined by high-performance liquid chromatography. The experimental parameters, including type and volume of extraction solvent, ultrasonication time, volume of hexane and eluting solvent, amount of MIL-101(Cr) and dispersive solid phase extraction time, were optimized. The limits of detection for herbicides range from 0.98 to 1.9 μg/kg. The recoveries of the herbicides are in the range of 89.5-102.7% and relative standard deviations are equal or lower than 7.0%. The proposed method is simple, effective and suitable for treatment of the samples containing high content of fat.

  16. Role of sediment resuspension in the remobilization of particulate-phase metals from coastal sediments

    Science.gov (United States)

    Kalnejais, Linda H.; Martin, William R.; Signell, Richard P.; Bothner, Michael H.

    2007-01-01

    The release of particulate-phase trace metals due to sediment resuspension has been investigated by combining erosion chamber experiments that apply a range of shear stresses typically encountered in coastal environments with a shear stress record simulated by a hydrodynamic model. Two sites with contrasting sediment chemistry were investigated. Sediment particles enriched in silver, copper, and lead, 4−50 times greater than the bulk surface-sediment content, were the first particles to be eroded. As the shear-stress level was increased in the chamber, the total mass eroded increased, but the enrichment of these trace metals fell, approaching the bulk-sediment content. From the temporal distribution of shear stress generated by the hydrodynamic model for a site in Boston Harbor, resuspension fluxes were estimated. The erosion threshold of this site is exceeded during spring tides, releasing the particles enriched in trace metals into the water column. Due to the higher trace metal content and the regularity of resuspension, low-energy resuspension events (up to a shear stress of 0.2 N/m2) contribute up to 60% of the resuspension metal flux in an average year. The estimated annual quantity of copper and lead resuspended into the water column is higher than estimates of the total riverine flux for these metals. These results indicate that sediment resuspension is a very important mechanism for releasing metals into the water column and provide new insight into the chemical and physical processes controlling the long-term fate of trace metals in contaminated sediments.

  17. Striped nanoscale phase separation at the metal-insulator transition of heteroepitaxial nickelates

    Science.gov (United States)

    Mattoni, G.; Zubko, P.; Maccherozzi, F.; van der Torren, A. J. H.; Boltje, D. B.; Hadjimichael, M.; Manca, N.; Catalano, S.; Gibert, M.; Liu, Y.; Aarts, J.; Triscone, J.-M.; Dhesi, S. S.; Caviglia, A. D.

    2016-11-01

    Nucleation processes of mixed-phase states are an intrinsic characteristic of first-order phase transitions, typically related to local symmetry breaking. Direct observation of emerging mixed-phase regions in materials showing a first-order metal-insulator transition (MIT) offers unique opportunities to uncover their driving mechanism. Using photoemission electron microscopy, we image the nanoscale formation and growth of insulating domains across the temperature-driven MIT in NdNiO3 epitaxial thin films. Heteroepitaxy is found to strongly determine the nanoscale nature of the phase transition, inducing preferential formation of striped domains along the terraces of atomically flat stepped surfaces. We show that the distribution of transition temperatures is a local property, set by surface morphology and stable across multiple temperature cycles. Our data provide new insights into the MIT of heteroepitaxial nickelates and point to a rich, nanoscale phenomenology in this strongly correlated material.

  18. Dynamical Piezoelectric and Magnetopiezoelectric Effects in Polar Metals from Berry Phases and Orbital Moments

    Science.gov (United States)

    Varjas, Dániel; Grushin, Adolfo G.; Ilan, Roni; Moore, Joel E.

    2016-12-01

    The polarization of a material and its response to applied electric and magnetic fields are key solid-state properties with a long history in insulators, although a satisfactory theory required new concepts such as Berry-phase gauge fields. In metals, quantities such as static polarization and the magnetoelectric θ term cease to be well defined. In polar metals, there can be analogous dynamical current responses, which we study in a common theoretical framework. We find that current responses to dynamical strain in polar metals depend on both the first and second Chern forms, related to polarization and magnetoelectricity in insulators as well as the orbital magnetization on the Fermi surface. We provide realistic estimates that predict that the latter contribution will dominate, and we investigate the feasibility of experimental detection of this effect.

  19. Separation of heavy metals from water by functionalized glycidyl methacrylate poly (high internal phase emulsions).

    Science.gov (United States)

    Huš, Sebastjan; Kolar, Mitja; Krajnc, Peter

    2016-03-11

    Removal of silver, lead and cadmium ions from both model solutions and real contaminated water was achieved, in a flow through manner, by using highly porous functionalized poly(glycidyl methacrylate) materials, prepared by the polymerisation of high internal phase emulsions (polyHIPE), with significant sorption differences between metals allowing for selective removal. PolyHIPEs, initially prepared from glycidyl methacrylate as a functional monomer, were functionalized with pentaerythritol tetrakis(3-mercaptopropionate), 1,9-nonanedithiol and 2-aminobenzenethiol via the epoxy ring opening on the polymer supports and applied in a flow-through manner via encasements into dedicated disk holders. Capacity of 21.7mg Ag per gram of polymer was found for 1,9-nonanedithiol functionalized polymers, while the capacity was decreasing with the decreasing ionic radius of the metal; the dynamics of sorption also depended on metal ion size and furthermore on the thiol used for the polymer functionalization.

  20. Phase field crystal modelling of the order-to-disordered atomistic structure transition of metallic glasses

    Science.gov (United States)

    Zhang, W.; Mi, J.

    2016-03-01

    Bulk metallic glass composites are a new class of metallic alloy systems that have very high tensile strength, ductility and fracture toughness. This unique combination of mechanical properties is largely determined by the presence of crystalline phases uniformly distributed within the glassy matrix. However, there have been very limited reports on how the crystalline phases are nucleated in the super-cooled liquid and their growth dynamics, especially lack of information on the order-to-disordered atomistic structure transition across the crystalline-amorphous interface. In this paper, we use phase field crystal (PFC) method to study the nucleation and growth of the crystalline phases and the glass formation of the super cooled liquid of a binary alloy. The study is focused on understanding the order-to-disordered transition of atomistic configuration across the interface between the crystalline phases and amorphous matrix of different chemical compositions at different thermal conditions. The capability of using PFC to simulate the order-to-disorder atomistic transition in the bulk material or across the interface is discussed in details.