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Sample records for alkali halides doped

  1. Alkali metal and alkali earth metal gadolinium halide scintillators

    DOEpatents

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

    2016-08-02

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

  2. Adsorption on Alkali Halides.

    NASA Astrophysics Data System (ADS)

    Urzua Duran, Gilberto Antonio

    1995-01-01

    Using a variety of interionic potentials, I have computed the configurations of adsorbed alkali halides monomers on the (001) surface of selected alkali halides crystals. In the majority of cases studied it is found that the monomer adsorbs perpendicular to the surface with the cation sitting nearly on top of the surface anion. In about ten percent of the cases though the monomer adsorbs tilted from the vertical. In these cases the ion that is closer to the surface can be the cation or the anion. The effect of polarization forces is found to be important. In order to discuss the effects of surface retaxation with adsorbates, I have evaluated the surface relaxation of the alkali halide crystals, using a shell model for the interionic forces. It is found that surface relaxation and rumpling are generally small, especially when the van der Waals forces are included. A theory of the effect of substrate vibrations on the binding of an adsorbed atom is developed. At T = 0 the binding energy is D_0-E, where D_0 is the surface well depth (classical binding energy) and E is the quantum correction. For several simple models, it is found that E is surprisingly model-independent. We compare D _0-E with the binding energies to a rigid substrate, D_0-E_{rs}, and to a vibrationally averaged substrate, D _0-E_{va}. We prove that E_{va}>=q E>=q E_ {rs} and that similar relations hold at finite temperature for the free energy of binding. In most cases E_{rs} is better than E_{va} as an approximation to E.

  3. Relation between the electroforming voltage in alkali halide-polymer diodes and the bandgap of the alkali halide

    SciTech Connect

    Bory, Benjamin F.; Wang, Jingxin; Janssen, René A. J.; Meskers, Stefan C. J.; Gomes, Henrique L.; De Leeuw, Dago M.

    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.

  4. The Additive Coloration of Alkali Halides

    ERIC Educational Resources Information Center

    Jirgal, G. H.; and others

    1969-01-01

    Describes the construction and use of an inexpensive, vacuum furnace designed to produce F-centers in alkali halide crystals by additive coloration. The method described avoids corrosion or contamination during the coloration process. Examination of the resultant crystals is discussed and several experiments using additively colored crystals are…

  5. Ionic alkali halide XUV laser feasibility study

    SciTech Connect

    Yang, T.T.; Gylys, V.T.; Bower, R.D.; Harris, D.G.; Blauer, J.A.; Turner, C.E.; Hindy, R.N.

    1989-11-10

    The objective of this work is to assess the feasibility of a select set of ionic alkali halide XUV laser concepts by obtaining the relevant kinetic and spectroscopic parameters required for a proof-of-principle and conceptual design. The proposed lasers operate in the 80--200 nm spectral region and do not require input from outside radiation sources for their operation. Frequency up-conversion and frequency mixing techniques and therefore not considered in the work to be described. An experimental and theoretical study of a new type of laser operating in the extreme ultraviolet wavelength region has been conducted. The lasing species are singly ionized alkali halide molecules such as Rb{sup 2+}F{sub {minus}}, Rb{sup 2+}Br{sup {minus}} and Cs{sup 2+}F{sup {minus}}. These species are similar in electronic structure to the rare gas halide excimers, such as XeF and Krf, except that the ionic molecules emit at wavelengths of 80--200 nm, much shorter than the conventional rare-gas halide excimer laser. The radiative lifetime of these molecules are typically near 1 ns, which is about an order of magnitude shorter than that for rare-gas halide systems. The values of the cross section for stimulated emission are on the order of 1 {times} 10{sup {minus}16}cm{sup 2}. Because of the fundamental similarity to existing UV lasers, these systems show promise as a high power, efficient XUV lasers. 55 refs., 50 figs., 5 tabs.

  6. Electro-optic contribution to Raman scattering from alkali halides

    SciTech Connect

    Mahan, G.D.; Subbaswamy, K.R.

    1986-06-15

    The electro-optic contributions to second-order Raman scattering and field-induced first-order scattering from alkali halides are calculated explicitly in terms of the ionic hyperpolarizability coefficients. The relevant local-field corrections are evaluated. Illustrative numerical results are presented.

  7. Cohesive Energy-Lattice Constant and Bulk Modulus-Lattice Constant Relationships: Alkali Halides, Ag Halides, Tl Halides

    NASA Technical Reports Server (NTRS)

    Schlosser, Herbert

    1992-01-01

    In this note we present two expressions relating the cohesive energy, E(sub coh), and the zero pressure isothermal bulk modulus, B(sub 0), of the alkali halides. Ag halides and TI halides, with the nearest neighbor distances, d(sub nn). First, we show that the product E(sub coh)d(sub 0) within families of halide crystals with common crystal structure is to a good approximation constant, with maximum rms deviation of plus or minus 2%. Secondly, we demonstrate that within families of halide crystals with a common cation and common crystal structure the product B(sub 0)d(sup 3.5)(sub nn) is a good approximation constant, with maximum rms deviation of plus or minus 1.36%.

  8. Interfacial tension in immiscible mixtures of alkali halides.

    PubMed

    Lockett, Vera; Rukavishnikova, Irina V; Stepanov, Victor P; Tkachev, Nikolai K

    2010-02-01

    The interfacial tension of the liquid-phase interface in seven immiscible reciprocal ternary mixtures of lithium fluoride with the following alkali halides: CsCl, KBr, RbBr, CsBr, KI, RbI, and CsI was measured using the cylinder weighing method over a wide temperature range. It was shown that for all mixtures the interfacial tension gradually decreases with growing temperature. The interfacial tension of the reciprocal ternary mixtures at a given temperature increases both with the alkali cation radius (K(+) < Rb(+) < Cs(+)) and with the radius of the halogen anion (Cl(-) < Br(-) < I(-)). PMID:20094678

  9. Alkali Halide Microstructured Optical Fiber for X-Ray Detection

    NASA Technical Reports Server (NTRS)

    DeHaven, S. L.; Wincheski, R. A.; Albin, S.

    2014-01-01

    Microstructured optical fibers containing alkali halide scintillation materials of CsI(Na), CsI(Tl), and NaI(Tl) are presented. The scintillation materials are grown inside the microstructured fibers using a modified Bridgman-Stockbarger technique. The x-ray photon counts of these fibers, with and without an aluminum film coating are compared to the output of a collimated CdTe solid state detector over an energy range from 10 to 40 keV. The photon count results show significant variations in the fiber output based on the materials. The alkali halide fiber output can exceed that of the CdTe detector, dependent upon photon counter efficiency and fiber configuration. The results and associated materials difference are discussed.

  10. Alkali halide microstructured optical fiber for X-ray detection

    SciTech Connect

    DeHaven, S. L. E-mail: russel.a.wincheski@nasa.gov; Wincheski, R. A. E-mail: russel.a.wincheski@nasa.gov; Albin, S.

    2015-03-31

    Microstructured optical fibers containing alkali halide scintillation materials of CsI(Na), CsI(Tl), and NaI(Tl) are presented. The scintillation materials are grown inside the microstructured fibers using a modified Bridgman-Stockbarger technique. The x-ray photon counts of these fibers, with and without an aluminum film coating are compared to the output of a collimated CdTe solid state detector over an energy range from 10 to 40 keV. The photon count results show significant variations in the fiber output based on the materials. The alkali halide fiber output can exceed that of the CdTe detector, dependent upon photon counter efficiency and fiber configuration. The results and associated materials difference are discussed.

  11. Volcanic Origin of Alkali Halides on Io

    NASA Technical Reports Server (NTRS)

    Schaefer, L.; Fegley, B., Jr.

    2003-01-01

    The recent observation of NaCl (gas) on Io confirms our earlier prediction that NaCl is produced volcanically. Here we extend our calculations by modeling thermochemical equilibrium of O, S, Li, Na, K, Rb, Cs, F, Cl, Br, and I as a function of temperature and pressure in a Pele-like volcanic gas with O/S/Na/Cl/K = 1.518/1/0.05/0.04/0.005 and CI chondritic ratios of the other (as yet unobserved) alkalis and halogens. For reference, the nominal temperature and pressure for Pele is 1760 plus or minus 210 K and 0.01 bars based on Galileo data and modeling.

  12. Electronic excitation in bulk and nanocrystalline alkali halides.

    PubMed

    Bichoutskaia, Elena; Pyper, Nicholas C

    2012-11-14

    The lowest energy excitations in bulk alkali halides are investigated by considering five different excited state descriptions. It is concluded that excitation transfers one outermost halide electron in the fully ionic ground state to the lowest energy vacant s orbital of one closest cation neighbour to produce the excited state termed dipolar. The excitation energies of seven salts were computed using shell model description of the lattice polarization produced by the effective dipole moment of the excited state neutral halogen-neutral metal pair. Ab initio uncorrelated short-range inter-ionic interactions computed from anion wavefunctions adapted to the in-crystal environment were augmented by short-range electron correlation contributions derived from uniform electron-gas density functional theory. Dispersive attractions including wavefunction overlap damping were introduced using reliable semi-empirical dispersion coefficients. The good agreement between the predicted excitation energies and experiment provides strong evidence that the excited state is dipolar. In alkali halide nanocrystals in which each ionic plane contains only four ions, the Madelung energies are significantly reduced compared with the bulk. This predicts that the corresponding intra-crystal excitation energies in the nanocrystals, where there are two excited states depending on whether the halide electron is transferred to a cation in the same or in the neighbouring plane, will be reduced by almost 2 eV. For such an encapsulated KI crystal, it has been shown that the greater polarization in the excited state of the bulk crystal causes these reductions to be lowered to a 1.1 eV-1.5 eV range for the case of charge transfer to a neighbouring plane. For intra-plane charge transfer the magnitude of the polarization energy is further reduced thus causing the excitation in these encapsulated materials to be only 0.2 eV less than in the bulk crystal. PMID:23163361

  13. A new mechanism for radiation damage processes in alkali halides

    NASA Astrophysics Data System (ADS)

    Dubinko, V. I.; Turkin, A. A.; Vainshtein, D. I.; den Hartog, H. W.

    1999-12-01

    We present a theory of radiation damage formation in alkali halides based on a new mechanism of dislocation climb, which involves the production of VF centers (self-trapped hole neighboring a cation vacancy) as a result of the absorption of H centers of dislocation lines. We consider the evolution of all experimentally observed extended defects: metal colloids, gas bubbles, and vacancy voids. Voids are shown to arise and grow large due to the reaction between F and VF centers at the surface of halogen bubbles. Voids can ignite a back reaction between the radiolytic products resulting in decomposition of the irradiated material.

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

    PubMed

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

    2016-09-01

    A new method was developed for doping and fabricating hysteresis-free hybrid perovskite-based photovoltaic devices by using alkali metal halide salts as interface layer additives. Such salt layers introduced at the perovskite interface can provide excessive halide ions to fill vacancies formed during the deposition and annealing process. A range of solution-processed halide salts were investigated. The highest performance of methylammonium lead mixed-halide perovskite device was achieved with a NaI interlayer and showed a power conversion efficiency of 12.6% and a hysteresis of less than 2%. This represents a 90% improvement compared to control devices without this salt layer. Through depth-resolved mass spectrometry, optical modeling, and photoluminescence spectroscopy, this enhancement is attributed to the reduction of iodide vacancies, passivation of grain boundaries, and improved hole extraction. Our approach ultimately provides an alternative and facile route to high-performance and hysteresis-free perovskite solar cells. PMID:27532662

  15. A new polarizable force field for alkali and halide ions

    SciTech Connect

    Kiss, Péter T.; Baranyai, András

    2014-09-21

    We developed transferable potentials for alkali and halide ions which are consistent with our recent model of water [P. T. Kiss and A. Baranyai, J. Chem. Phys. 138, 204507 (2013)]. Following the approach used for the water potential, we applied Gaussian charge distributions, exponential repulsion, and r{sup −6} attraction. One of the two charges of the ions is fixed to the center of the particle, while the other is connected to this charge by a harmonic spring to express polarization. Polarizability is taken from quantum chemical calculations. The repulsion between different species is expressed by the combining rule of Kong [J. Chem. Phys. 59, 2464 (1972)]. Our primary target was the hydration free energy of ions which is correct within the error of calculations. We calculated water-ion clusters up to 6 water molecules, and, as a crosscheck, we determined the density and internal energy of alkali-halide crystals at ambient conditions with acceptable accuracy. The structure of hydrated ions was also discussed.

  16. A new polarizable force field for alkali and halide ions

    NASA Astrophysics Data System (ADS)

    Kiss, Péter T.; Baranyai, András

    2014-09-01

    We developed transferable potentials for alkali and halide ions which are consistent with our recent model of water [P. T. Kiss and A. Baranyai, J. Chem. Phys. 138, 204507 (2013)]. Following the approach used for the water potential, we applied Gaussian charge distributions, exponential repulsion, and r-6 attraction. One of the two charges of the ions is fixed to the center of the particle, while the other is connected to this charge by a harmonic spring to express polarization. Polarizability is taken from quantum chemical calculations. The repulsion between different species is expressed by the combining rule of Kong [J. Chem. Phys. 59, 2464 (1972)]. Our primary target was the hydration free energy of ions which is correct within the error of calculations. We calculated water-ion clusters up to 6 water molecules, and, as a crosscheck, we determined the density and internal energy of alkali-halide crystals at ambient conditions with acceptable accuracy. The structure of hydrated ions was also discussed.

  17. Studies of Non-Proportionality in Alkali Halide and Strontium Iodide Scintillators Using SLYNCI

    SciTech Connect

    Ahle, L; Bizarri, G; Boatner, L; Cherepy, N J; Choong, W; Moses, W W; Payne, S A; Shah, K; Sheets, S; Sturm, B W

    2009-05-05

    Recently a collaboration of LLNL and LBNL has constructed a second generation Compton coincidence instrument to study the non-proportionality of scintillators [1-3]. This device, known as SLYNCI (Scintillator Light-Yield Non-proportionality Characterization Instrument), has can completely characterize a sample with less than 24 hours of running time. Thus, SLYNCI enables a number of systematic studies of scintillators since many samples can be processed in a reasonable length of time. These studies include differences in nonproportionality between different types of scintillators, different members of the same family of scintillators, and impact of different doping levels. The results of such recent studies are presented here, including a study of various alkali halides, and the impact of europium doping level in strontium iodide. Directions of future work area also discussed.

  18. Studies of non-proportionality in alkali halide and strontium iodide scintillators using SLYNCI

    SciTech Connect

    Ahle, Larry; Bizarri, Gregory; Boatner, Lynn; Cherepy, Nerine J.; Choong, Woon-Seng; Moses, William W.; Payne, Stephen A.; Shah, Kanai; Sheets, Steven; Sturm, Benjamin, W.

    2010-10-14

    Recently a collaboration of LLNL and LBNL has constructed a second generation Compton coincidence instrument to study the non-proportionality of scintillators. This device, known as SLYNCI (Scintillator Light-Yield Non-proportionality Characterization Instrument), has can completely characterize a sample with less than 24 hours of running time. Thus, SLYNCI enables a number of systematic studies of scintillators since many samples can be processed in a reasonable length of time. These studies include differences in nonproportionality between different types of scintillators, different members of the same family of scintillators, and impact of different doping levels. The results of such recent studies are presented here, including a study of various alkali halides, and the impact of europium doping level in strontium iodide. Directions of future work area also discussed.

  19. Lanthanide doped strontium-barium cesium halide scintillators

    SciTech Connect

    Bizarri, Gregory; Bourret-Courchesne, Edith; Derenzo, Stephen E.; Borade, Ramesh B.; Gundiah, Gautam; Yan, Zewu; Hanrahan, Stephen M.; Chaudhry, Anurag; Canning, Andrew

    2015-06-09

    The present invention provides for a composition comprising an inorganic scintillator comprising an optionally lanthanide-doped strontium-barium, optionally cesium, halide, useful for detecting nuclear material.

  20. Potential function and dissociation energy of alkali halide

    NASA Astrophysics Data System (ADS)

    Srivastava, Abhay P.; Pandey, Anjani K.; Pandey, Brijesh K.

    2016-05-01

    Dissociation energy of some alkali halides have been calculated by using different interaction potential function such as Born-Mayer, Varshani-Shukla and L5 potential model. The theoretical calculation is compared with experimental values. The Result shows that the values of dissociation energy as calculated by using different potential models have an equal amount of deviation with experimental values. The above said deviation with experimental values can be explained by consideration of rotational-vibrational coupling between the constituents of molecules in the limelight of molecular spectroscopy. Findings of present work suggest that the existing potential model need to be reviewed in view of the correction factors solely depending on the rotational, vibrational and electronic coupling between the constituents of molecules.

  1. Fabrication of alkali halide UV photocathodes by pulsed laser deposition

    SciTech Connect

    Brendel', V M; Bukin, V V; Garnov, Sergei V; Bagdasarov, V Kh; Denisov, N N; Garanin, Sergey G; Terekhin, V A; Trutnev, Yurii A

    2012-12-31

    A technique has been proposed for the fabrication of atmospheric corrosion resistant alkali halide UV photocathodes by pulsed laser deposition. We produced photocathodes with a highly homogeneous photoemissive layer well-adherent to the substrate. The photocathodes were mounted in a vacuum photodiode, and a tungsten grid was used as an anode. Using pulsed UV lasers, we carried out experiments aimed at evaluating the quantum efficiency of the photocathodes. With a dc voltage applied between the photocathode and anode grid, we measured a shunt signal proportional to the total charge emitted by the cathode exposed to UV laser light. The proposed deposition technique enables one to produce photocathodes with photoemissive layers highly uniform in quantum efficiency, which is its main advantage over thin film growth by resistive evaporation. (laser technologies)

  2. Fabrication of alkali halide UV photocathodes by pulsed laser deposition

    NASA Astrophysics Data System (ADS)

    Brendel', V. M.; Bukin, V. V.; Garnov, Sergei V.; Bagdasarov, V. Kh; Denisov, N. N.; Garanin, Sergey G.; Terekhin, V. A.; Trutnev, Yurii A.

    2012-12-01

    A technique has been proposed for the fabrication of atmospheric corrosion resistant alkali halide UV photocathodes by pulsed laser deposition. We produced photocathodes with a highly homogeneous photoemissive layer well-adherent to the substrate. The photocathodes were mounted in a vacuum photodiode, and a tungsten grid was used as an anode. Using pulsed UV lasers, we carried out experiments aimed at evaluating the quantum efficiency of the photocathodes. With a dc voltage applied between the photocathode and anode grid, we measured a shunt signal proportional to the total charge emitted by the cathode exposed to UV laser light. The proposed deposition technique enables one to produce photocathodes with photoemissive layers highly uniform in quantum efficiency, which is its main advantage over thin film growth by resistive evaporation.

  3. Solvent-averaged potentials for alkali-, earth alkali-, and alkylammonium halide aqueous solutions

    NASA Astrophysics Data System (ADS)

    Hess, Berk; van der Vegt, Nico F. A.

    2007-12-01

    We derive effective, solvent-free ion-ion potentials for alkali-, earth alkali-, and alkylammonium halide aqueous solutions. The implicit solvent potentials are parametrized to reproduce experimental osmotic coefficients. The modeling approach minimizes the amount of input required from atomistic (force field) models, which usually predict large variations in the effective ion-ion potentials at short distances. For the smaller ion species, the reported potentials are composed of a Coulomb and a Weeks-Chandler-Andersen term. For larger ions, we find that an additional, attractive potential is required at the contact minimum, which is related to solvent degrees of freedom that are usually not accounted for in standard electrostatics models. The reported potentials provide a simple and accurate force field for use in molecular dynamics and Monte Carlo simulations of (poly-)electrolyte systems.

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

    PubMed

    Lee, Myung Churl; Choi, Wonyong

    2002-03-15

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

  5. Investigating Metallization in Shock-Compressed Alkali Halides

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  6. Strong Turbulence in Alkali Halide Negative Ion Plasmas

    NASA Astrophysics Data System (ADS)

    Sheehan, Daniel

    1999-11-01

    Negative ion plasmas (NIPs) are charge-neutral plasmas in which the negative charge is dominated by negative ions rather than electrons. They are found in laser discharges, combustion products, semiconductor manufacturing processes, stellar atmospheres, pulsar magnetospheres, and the Earth's ionosphere, both naturally and man-made. They often display signatures of strong turbulence^1. Development of a novel, compact, unmagnetized alkali halide (MX) NIP source will be discussed, it incorporating a ohmically-heated incandescent (2500K) tantulum solenoid (3cm dia, 15 cm long) with heat shields. The solenoid ionizes the MX vapor and confines contaminant electrons, allowing a very dry (electron-free) source. Plasma densities of 10^10 cm-3 and positive to negative ion mass ratios of 1 <= fracm_+m- <= 20 are achievable. The source will allow tests of strong turbulence theory^2. 1 Sheehan, D.P., et al., Phys. Fluids B5, 1593 (1993). 2 Tsytovich, V. and Wharton, C.W., Comm. Plasma Phys. Cont. Fusion 4, 91 (1978).

  7. Reflectivities of Four Shock-Compressed Alkali Halides

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

    Laser-shock compression on four alkali halides has been used to probe the transition from insulating to metallic states, a high-pressure transition in chemical bonding that has fundamental implications for planetary formation and structure. Collectively, pressures up to 450 GPa and densities up to three-fold compression were explored across a total of fourteen single-crystal samples of CsI, CsBr, KBr and NaCl. Velocity interferometry was used to record shock velocities and reflectivities at 532 nm during decaying shock compression. The data show up to 40% (or higher) reflectivity, corresponding to notable electrical conductivities, in response to high pressures and temperatures. Furthermore, band-gap closure, dependent on density, can be examined from the reflectivity data. Ionic salts are simple model systems amenable to first-principles theory and serve as analog materials for predicting whether specific chemical constituents can reside in the rocky mantles or metallic cores of planets. A key objective is to disentangle the complementary roles of temperature and compression in transforming ionic into metallic bonding. Furthermore, at high pressures CsI becomes analogous to Xe: they are isoelectronic and follow matching equations of state. Therefore, studies on CsI could inform understanding of noble-gas geochemistry at conditions deep inside planets.

  8. Superconductivity in alkali-doped C60

    NASA Astrophysics Data System (ADS)

    Ramirez, Arthur P.

    2015-07-01

    Superconductivity in alkali-doped C60 (A3C60, A = an alkali atom) is well described by an s-wave state produced by phonon mediated pairing. Moderate coupling of electrons to high-frequency shape-changing intra-molecular vibrational modes produces transition temperatures (Tc) up to 33 K in single-phase material. The good understanding of pairing in A3C60 offers a paradigm for the development of new superconducting materials.

  9. Graphitic cage transformation by electron-beam-induced catalysis with alkali-halide nanocrystals

    NASA Astrophysics Data System (ADS)

    Fujita, Jun-ichi; Tachi, Masashi; Ito, Naoto; Murakami, Katsuhisa; Takeguchi, Masaki

    2016-05-01

    We found that alkali-halide nanocrystals, such as KCl and NaCl, have strong catalytic capability to form graphitic carbon cages from amorphous carbon shells under electron beam irradiation. In addition to the electron beam irradiation strongly inducing the decomposition of alkali-halide nanocrystals, graphene fragments were formed and linked together to form the final product of thin graphitic carbon cages after the evaporation of alkali-halide nanocrystals. The required electron dose was approximately 1 to 20 C/cm2 at 120 keV at room temperature, which was about two orders of magnitude smaller than that required for conventional beam-induced graphitization. The “knock-on” effect of primary electrons strongly induced the decomposition of the alkali-halide crystal inside the amorphous carbon shell. However, the strong ionic cohesion quickly reformed the crystal into thin layers inside the amorphous shell. The bond excitation induced by the electron beam irradiation seemed to enhance strongly the graphitization at the interface between the outer amorphous carbon shell and the inner alkali-halide crystal.

  10. Theoretical and experimental investigation of force imaging at the atomic scale on alkali halide crystals

    NASA Astrophysics Data System (ADS)

    Shluger, A. L.; Wilson, R. Mark; Williams, R. T.

    1994-02-01

    Assuming a model tip (Si4O10H10) as a reasonable representation of the surface of a Si3N4 cantilever stylus having a hydrogen-terminated asperity and a broader load-bearing base, we investigate the interaction of an atomic force microscope (AFM) with an alkali halide crystal by quantum chemical methods. Structural relaxation of the sample during engagement is allowed, and defect formation is investigated. Force curves above cation and anion positions are calculated, determining maximum sustainable loads and indicating a basis for atomic contrast. Experiments using a Si3N4 cantilever for AFM imaging of 12 alkali halide and alkaline earth fluoride crystals in air and desiccated helium are reported, in the widest AFM survey of such materials to date. Adsorbed water is shown to significantly enhance the observation of atomic periodicity on ionic halide samples, and rapid surface diffusion on alkali halide crystals is illustrated as it affects prospects for defect investigations. Observations of step edges and point-defect candidates at atomic scale are reported. The theoretical and experimental results are discussed together in the effort to provide a quantum-mechanical model for observations of alkali halide samples at atomic resolution, and to examine a possible basis for atomic resolution in the presence of long-range attractive forces.

  11. Electro-optic contribution to field-induced Raman scattering in alkali halides

    SciTech Connect

    Subbaswamy, K.R.; Mahan, G.D.

    1985-10-15

    The electro-optic contribution to the field-induced first-order Raman scattering cross section in alkali halide crystals is calculated using measured values for hyperpolarizabilities. The electro-optic contribution is much larger than the previously reported atomic displacement contribution. The results cast some doubt on the accuracy of the reported hyperpolarizability values.

  12. Resonance-Raman-scattering spectroscopy for the halogen-molecular-ion centers in alkali halides

    NASA Astrophysics Data System (ADS)

    Suzuki, T.; Tanimura, K.; Itoh, N.

    1993-10-01

    We have measured the Raman scattering in resonance with the bonding-to-antibonding transitions of two types of dihalogen-molecular-ion centers in alkali halides, the VK and H centers; the molecular ion occupies two adjacent halogen sites in the former and a single halogen site in the latter. It is found that the stretching-vibration frequency of the molecular ion is higher by more than 30% for the H center than for the VK center. The hardening is ascribed to the bond tightening due to the Madelung potential. Although the Raman line due to the stretching vibration consists of a single line in most alkali halides, two closely lying lines are observed for the H centers in alkali halides with small alkali-metal to halogen radius ratio and also for the VK center in NaCl. The paired-line structure is ascribed to the coupling of the stretching vibration of the halogen molecular ion with the lattice.

  13. Refined potentials for rare gas atom adsorption on rare gas and alkali-halide surfaces

    NASA Technical Reports Server (NTRS)

    Wilson, J. W.; Heinbockel, J. H.; Outlaw, R. A.

    1985-01-01

    The utilization of models of interatomic potential for physical interaction to estimate the long range attractive potential for rare gases and ions is discussed. The long range attractive force is calculated in terms of the atomic dispersion properties. A data base of atomic dispersion parameters for rare gas atoms, alkali ion, and halogen ions is applied to the study of the repulsive core; the procedure for evaluating the repulsive core of ion interactions is described. The interaction of rare gas atoms on ideal rare gas solid and alkali-halide surfaces is analyzed; zero coverage absorption potentials are derived.

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

    NASA Technical Reports Server (NTRS)

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

    1982-01-01

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

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

    SciTech Connect

    Lutz, Jesse J.; Hutson, Jeremy M.

    2014-01-07

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

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

    NASA Technical Reports Server (NTRS)

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

    1980-01-01

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

  17. Theoretical analysis of the kinetics of low-temperature defect recombination in alkali halide crystals

    NASA Astrophysics Data System (ADS)

    Kuzovkov, V. N.; Popov, A. I.; Kotomin, E. A.; Moskina, A. M.; Vasilchenko, E.; Lushchik, A.

    2016-07-01

    We analyzed carefully the experimental kinetics of the low-temperature diffusion-controlled F, H center recombination in a series of irradiated alkali halides and extracted the migration energies and pre-exponential parameters for the hole H centers. The migration energy for the complementary electronic F centers in NaCl was obtained from the colloid formation kinetics observed above room temperature. The obtained parameters were compared with data available from the literature.

  18. Temperature Dependence of Interatomic Separation and Bulk Modulus for Alkali Halides

    NASA Astrophysics Data System (ADS)

    Liu, Quan

    2016-07-01

    The values of interatomic separation r with the change of temperature T for seven alkali halides have been investigated with the help of an isobaric equation of state. The calculated results are used to predict the values of bulk modulus at different temperatures. The results are compared with the available experimental data and other theoretical results and are further discussed in view of recent research in the field of high temperature physics.

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

    NASA Technical Reports Server (NTRS)

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

    1986-01-01

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

  20. Skylab experiments on semiconductors and alkali halides. [single crystal growth

    NASA Technical Reports Server (NTRS)

    Lundquist, C. A.

    1974-01-01

    The space processing experiments performed during the Skylab missions included one on single crystal growth of germanium selenide and telluride, one on pure and doped germanium crystals, two on pure and doped indium antimonide, one on gallium-indium-antimony systems, and one on a sodium chloride-sodium fluoride eutectic. In each experiment, three ampoules of sample were processed in the multipurpose electric furnace within the Skylab Materials Processing Facility. All were successful in varying degrees and gave important information about crystal growth removed from the effects of earth surface gravity.

  1. Unconventional Superconductivity of Alkali-doped Fullerenes

    NASA Astrophysics Data System (ADS)

    Potocnik, Anton; Krajnc, Andraz; Jeglic, Peter; Prassides, Kosmas; Rosseinsky, Matthew J.; Arcon, Denis

    2014-03-01

    The superconductivity of the alkali-doped fullerenes (A3C60, A = alkali metal) has been so far discussed within the standard theory of superconductivity developed by Bardeen, Cooper and Shrieffer (BCS), even thought, they exhibit relatively high critical temperatures (up to Tc = 32 K). However, after our recent high-pressure measurements on Cs3C60 such description became questionable. We have shown that the superconducting phase of A3C60, in fact, borders the antiferromagnetic insulating phase (AFI), commonly observed for high-temperature superconductors like cuprates or pnictides. In addition, we also increased the maximal Tc to 38 K. To investigate this peculiar superconductivity close to the border with AFI state we employed nuclear magnetic resonance technique on Cs3-xRbxC60 and on Cs3C60 at various high pressures. Our results could not be correctly explained either by the standard BCS or the extended BCS that includes electron-electron repulsion interaction - the Migdal-Eliashberg theory. Far better agreement is obtained by the Dynamical Mean Field Theory. Due to similarity with other unconventional superconductors these results could also be relevant to other unconventional high-temperature superconductors.

  2. Superconductivity in alkali-doped fullerene nanowhiskers.

    PubMed

    Takeya, Hiroyuki; Konno, Toshio; Hirata, Chika; Wakahara, Takatsugu; Miyazawa, Kun'ichi; Yamaguchi, Takahide; Tanaka, Masashi; Takano, Yoshihiko

    2016-09-01

    Superconductivity in alkali metal-doped fullerene nanowhiskers (C60NWs) was observed in K3.3C60NWs, Rb3.0C60NWs and Cs2.0Rb1.0C60NWs with transition temperatures at 17, 25 and 26 K, respectively. Almost full shielding volume fraction (~80%) was observed in K3.3C60NWs when subjected to thermal treatment at 200 °C for a duration of 24 h. In contrast, the shielding fraction of Rb3.0C60NWs and Cs2.0Rb1.0C60NWs were calculated to be 8% and 6%, respectively. Here we report on an extensive investigation of the superconducting properties of these AC60NWs (A  =  K3.3, Rb3.0 and Cs2.0Rb1.0). These properties are compared to the ones reported on the corresponding conventional (single-crystal or powder) K-doped fullerene. We also evaluated the critical current densities of these C60NWs using the Bean model under an applied magnetic field up to 50 kOe. PMID:27385220

  3. Superconductivity in alkali-doped fullerene nanowhiskers

    NASA Astrophysics Data System (ADS)

    Takeya, Hiroyuki; Konno, Toshio; Hirata, Chika; Wakahara, Takatsugu; Miyazawa, Kun’ichi; Yamaguchi, Takahide; Tanaka, Masashi; Takano, Yoshihiko

    2016-09-01

    Superconductivity in alkali metal-doped fullerene nanowhiskers (C60NWs) was observed in K3.3C60NWs, Rb3.0C60NWs and Cs2.0Rb1.0C60NWs with transition temperatures at 17, 25 and 26 K, respectively. Almost full shielding volume fraction (~80%) was observed in K3.3C60NWs when subjected to thermal treatment at 200 °C for a duration of 24 h. In contrast, the shielding fraction of Rb3.0C60NWs and Cs2.0Rb1.0C60NWs were calculated to be 8% and 6%, respectively. Here we report on an extensive investigation of the superconducting properties of these AC60NWs (A  =  K3.3, Rb3.0 and Cs2.0Rb1.0). These properties are compared to the ones reported on the corresponding conventional (single-crystal or powder) K-doped fullerene. We also evaluated the critical current densities of these C60NWs using the Bean model under an applied magnetic field up to 50 kOe.

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

    NASA Technical Reports Server (NTRS)

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

    2006-01-01

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

  5. Molecular dispersion energy parameters for alkali and halide ions in aqueous solution.

    PubMed

    Reiser, S; Deublein, S; Vrabec, J; Hasse, H

    2014-01-28

    Thermodynamic properties of aqueous solutions containing alkali and halide ions are determined by molecular simulation. The following ions are studied: Li(+), Na(+), K(+), Rb(+), Cs(+), F(-), Cl(-), Br(-), and I(-). The employed ion force fields consist of one Lennard-Jones (LJ) site and one concentric point charge with a magnitude of ±1 e. The SPC/E model is used for water. The LJ size parameter of the ion models is taken from Deublein et al. [J. Chem. Phys. 136, 084501 (2012)], while the LJ energy parameter is determined in the present study based on experimental self-diffusion coefficient data of the alkali cations and the halide anions in aqueous solutions as well as the position of the first maximum of the radial distribution function of water around the ions. On the basis of these force field parameters, the electric conductivity, the hydration dynamics of water molecules around the ions, and the enthalpy of hydration is predicted. Considering a wide range of salinity, this study is conducted at temperatures of 293.15 and 298.15 K and a pressure of 1 bar. PMID:25669552

  6. Molecular dispersion energy parameters for alkali and halide ions in aqueous solution

    SciTech Connect

    Reiser, S.; Deublein, S.; Hasse, H.; Vrabec, J.

    2014-01-28

    Thermodynamic properties of aqueous solutions containing alkali and halide ions are determined by molecular simulation. The following ions are studied: Li{sup +}, Na{sup +}, K{sup +}, Rb{sup +}, Cs{sup +}, F{sup −}, Cl{sup −}, Br{sup −}, and I{sup −}. The employed ion force fields consist of one Lennard-Jones (LJ) site and one concentric point charge with a magnitude of ±1 e. The SPC/E model is used for water. The LJ size parameter of the ion models is taken from Deublein et al. [J. Chem. Phys. 136, 084501 (2012)], while the LJ energy parameter is determined in the present study based on experimental self-diffusion coefficient data of the alkali cations and the halide anions in aqueous solutions as well as the position of the first maximum of the radial distribution function of water around the ions. On the basis of these force field parameters, the electric conductivity, the hydration dynamics of water molecules around the ions, and the enthalpy of hydration is predicted. Considering a wide range of salinity, this study is conducted at temperatures of 293.15 and 298.15 K and a pressure of 1 bar.

  7. Photoelectron Spectroscopy of Alkali-Halide Cluster Anions Containing Excess Electrons

    NASA Astrophysics Data System (ADS)

    Fatemi, Darius James

    1995-01-01

    We have obtained photoelectron spectra for alkali -halide clusters containing excess electrons. These measurements demonstrate that the mode of electron accommodation and the cluster configuration depend on the sizes of the atomic ions comprising the aggregate. We also report on the role of the source temperature in determining the structures observed for a cluster. Photoelectron measurements of metal-rich alkali -halide clusters (MX)_{n}M _{m}^-(m >=q 2) suggest that the metallic and ionic components within each of these systems are separated from each other. This behavior is evident for n = 3,5 in clusters of cesium chloride and for n = 3,7,8,9 for sodium iodide clusters. We also studied the mixed species (NaI) _{n}Na_{m} OH^- and(NaI)_ {n}H_2O ^-. The (NaI)_{n} Na_{m}OH ^- clusters appear to contain the OH ^- ion in the same way a halogen anion would be accommodated. Photoelectron spectra of(NaI) _{n}H_2O ^- are consistent with adsorption of a water molecule on an edge of an ionic lattice.

  8. Alkali Halide Interfacial Behavior in a Sequence of Charged Slit Pores

    SciTech Connect

    Wander, Matthew C; Shuford, Kevin L

    2011-01-01

    In this paper, a variety of alkali halide, aqueous electrolyte solutions in contact with charged, planar-graphite slit-pores are simulated using classical molecular dynamics. Size trends in structure and transport properties are examined by varying the choice of ions among the alkali metal and halide series. As with the uncharged pores, system dynamics are driven by changes in water hydration behavior and specifically by variations in the number of hydrogen bonds per water molecule. Overall, the larger ions diffuse more rapidly under high surface charge conditions than the smaller ions. In particular, for the 1 nmslit, ion diffusivity increased by a factor of 4 compared to the uncharged case. Finally, a quantitative fit to the interfacial charge structure is presented, which confirms the presence of two distinct types of layers in an aqueous interface. This model indicates that the chemistry of the interface is able to create a small interfacial potential, and it shows how water molecules can rotate to increase charge separation in response to a surface potential.

  9. Multiple neutral alkali halide attachments onto oligosaccharides in electrospray ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Striegel, André M.; Timpa, Judy D.; Piotrowiak, Piotr; Cole, Richard B.

    1997-03-01

    Oligosaccharides perform essential functions in a variety of biological and agricultural processes. Recent approaches to characterization of these molecules by mass spectrometry have utilized mainly soft-ionization methods such as electrospray ionization (ESI) and thermospray (TS), as well as fast atom bombardment (FAB). The behavior of a series of maltooligosaccharides with [alpha]-(1 --> 4) linkages, maltose (G2) through maltoheptaose (G7), under ESI conditions, has been investigated here. The oligosaccharides were dissolved in N,N-dimethylacetamide containing lithium chloride (DMAc/LiCl) prior to analysis by ESI-MS. A highly unusual feature, evident in all mass spectra obtained using this solvent system, was the presence of multiple [`]neutral' salt attachments onto lithium adducts of the sugars. Resultant ions took the form of [Gx + Li + nLiCl+, where n may reach a value as high as eight. Compared to LiCl, the propensity for alkali halide attachment using other alkali chlorides or lithium halides was greatly reduced. An investigation of this phenomenon is presented in which the organic and inorganic portions of the employed solvent were systematically varied, and semi-empirical computer modeling was performed to better understand lithium coordination by the sugars.

  10. Alkali Halide Interfacial Behavior in a Sequence of Charged Slit Pores

    SciTech Connect

    Wander, Matthew C. F.; Shuford, Kevin L.

    2011-12-01

    In this paper, a variety of alkali halide, aqueous electrolyte solutions in contact with charged, planar-graphite slit-pores are simulated using classical molecular dynamics. Size trends in structure and transport properties are examined by varying the choice of ions among the alkali metal and halide series. As with the uncharged pores, system dynamics are driven by changes in water hydration behavior and specifically by variations in the number of hydrogen bonds per water molecule. Overall, the larger ions diffuse more rapidly under high surface charge conditions than the smaller ions. In particular, for the 1 nm slit, ion diffusivity increased by a factor of 4 compared to the uncharged case. Finally, a quantitative fit to the interfacial charge structure is presented, which confirms the presence of two distinct types of layers in an aqueous interface. This model indicates that the chemistry of the interface is able to create a small interfacial potential, and it shows how water molecules can rotate to increase charge separation in response to a surface potential.

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

    PubMed Central

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

    2012-01-01

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

  12. Silicon Halide-alkali Metal Flames as a Source of Solar Grade Silicon

    NASA Technical Reports Server (NTRS)

    Olson, D. B.; Gould, R. K.

    1979-01-01

    A program is presented which was aimed at determining the feasibility of using high temperature reactions of alkali metals and silicon halides to produce low cost solar-grade silicon. Experiments are being conducted to evaluate product separation and collection processes, measure heat release parameters for scaling purposes, and determine the effects of the reactants and/or products on materials of reactor construction. During the current reporting period, the results of heat release experiments were used to design and construct a new type of thick-wall graphite reactor to produce larger quantities of silicon. A reactor test facility was constructed. Material compatibility tests were performed for Na in contact with graphite and several coated graphites. All samples were rapidly degraded at T = 1200K, while samples retained structural strength at 1700K. Pyrolytic graphite coatings cracked and separated from substances in all cases.

  13. Ion Segregation and Deliquescence of Alkali Halide Nanocrystals on SiO2

    NASA Astrophysics Data System (ADS)

    Arima, Kenta; Jiang, Peng; Lin, Deng-Sung; Verdaguer, Albert; Salmeron, Miquel

    2009-08-01

    The adsorption of water on alkali halide (KBr, KCl, KF, NaCl) nanocrystals on SiO2 and their deliquescence was investigated as a function of relative humidity (RH) from 8% to near saturation by scanning polarization force microscopy. At low humidity, water adsorption solvates ions at the surface of the crystals and increases their mobility. This results in a large increase in the dielectric constant, which is manifested in an increase in the electrostatic force and in an increase in the apparent height of the nanocrystals. Above 58% RH, the diffusion of ions leads to Ostwald ripening, where larger nanocrystals grow at the expense of the smaller ones. At the deliquescence point, droplets were formed. For KBr, KCl, and NaCl, the droplets exhibit a negative surface potential relative to the surrounding region, which is indicative of the preferential segregation of anions to the air/solution interface.

  14. Role of excitons in electron- and photon-stimulated desorption of neutrals from alkali halides.

    PubMed

    Alexandrov, A; Piacentini, M; Zema, N; Felici, A C; Orlando, T M

    2001-01-15

    Low-energy (5-15 eV) electron- and photon-stimulated desorption of KI(100) yields I2P3/2 and 2P1/2 with hyperthermal (0.3 eV) and thermal velocity components. The desorption threshold for both components is 5.3 eV and is correlated with the gamma3/2-exciton long-wavelength edge. Exciton decay at the surface directly produces I2P3/2 and 2P1/2 with hyperthermal velocity and is in competition with self-trapping. Spin memory of the gamma-exciton hole-component is also evident in the hyperthermal channel. An exciton mediated desorption mechanism is presented which is general in alkali halides. PMID:11177874

  15. Ab initio perspective on the Mollwo-Ivey relation for F centers in alkali halides

    NASA Astrophysics Data System (ADS)

    Tiwald, Paul; Karsai, Ferenc; Laskowski, Robert; Gräfe, Stefanie; Blaha, Peter; Burgdörfer, Joachim; Wirtz, Ludger

    2015-10-01

    We revisit the well-known Mollwo-Ivey relation that describes the "universal" dependence of the absorption energies of F-type color centers on the lattice constant a of alkali-halide crystals, Eabs∝a-n. We perform both state-of-the-art ab initio quantum chemistry and post-DFT calculations of F-center absorption spectra. By "tuning" independently the lattice constant and the atomic species we show that the scaling with the lattice constant alone (keeping the elements fixed) would yield n =2 in agreement with the "particle-in-the-box" model. Keeping the lattice constant fixed and changing the atomic species enables us to quantify the ion-size effects which are shown to be responsible for the exponent n ≈1.8 .

  16. Ion Segregation and Deliquescence of Alkali Halide Nanocrystals on SiO2

    SciTech Connect

    Arima, Kenta; Jiang, Peng; Lin, Deng-Sung; Verdaguer, Albert; Salmeron, Miquel

    2009-08-11

    The adsorption of water on alkali halide (KBr, KCl, KF, NaCl) nanocrystals on SiO{sub 2} and their deliquescence was investigated as a function of relative humidity (RH) from 8% to near saturation by scanning polarization force microscopy. At low humidity, water adsorption solvates ions at the surface of the crystals and increases their mobility. This results in a large increase in the dielectric constant, which is manifested in an increase in the electrostatic force and in an increase in the apparent height of the nanocrystals. Above 58% RH, the diffusion of ions leads to Ostwald ripening, where larger nanocrystals grow at the expense of the smaller ones. At the deliquescence point, droplets were formed. For KBr, KCl, and NaCl, the droplets exhibit a negative surface potential relative to the surrounding region, which is indicative of the preferential segregation of anions to the air/solution interface.

  17. Acid and alkali doped PBI electrolyte in electrochemical system

    NASA Astrophysics Data System (ADS)

    Xing, Baozhong

    In this work the conductivity of blank PBI membrane, acid doped PBI and alkaline doped PBI was systematically studied. A new methodology for sorption kinetics study in electrolyte solution has been established by monitoring the conductivity change during the sorption process. The model of the doping process and mechanism of conductivity are proposed. The performance of PBI (doped under optimum conditions) in fuel cell as PEM was evaluated. The experimental results show that the blank PBI in acid solution is an ionic insulator. It clarified the long time confusion in this area. The acid doped PBI membrane is an ionic conductor. The conductivity increases with the concentration of the acid solution. In high concentration acid solution, the conductivity increases with the type of acid in the order: H2SO 4 > H3PO4 > HClO4 > HNO3 > HCl. The kinetics of the doping process was studied, by a continuous method. The ionic conductivity mechanism was established. The PBI membranes doped with H2SO4 and H3PO4 exhibit better performance than NafionRTM. The doped FBI has more resistance to CO poison. 3% CO in H2 has little effect on the H3PO 4 doped PBI membrane at 185°C. The conductivity of the alkali doped PBI membrane changes with the concentration of the alkaline solution and the type of the alkalis. The conductivity has a maximum in KOH and NaOH solution. The maximum conductivity in KOH is higher than in NaOH and LiOH. It is about 5 times of that of NafionRTM in alkaline solution. The two-step sorption process in alkaline solution was observed. The first step is the permeation process of the alkalis in the PBI membrane. The permeation is the results of diffusion and interaction. It is concluded that the permeation process is controlled by the rate of interaction between the alkali and PBI molecule. The second step is the relaxation process in the membrane. This step contributes more to the conductivity for the membrane than the first step. The ionic conductivity mechanism

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

    NASA Technical Reports Server (NTRS)

    Olsen, D. B.; Miller, W. J.

    1979-01-01

    The feasibility of using alkali metal-silicon halide diffusion flames to produce solar-grade silicon in large quantities and at low cost is demonstrated. Prior work shows that these flames are stable and that relatively high purity silicon can be produced using Na + SiCl4 flames. Silicon of similar purity is obtained from Na + SiF4 flames although yields are lower and product separation and collection are less thermochemically favored. Continuous separation of silicon from the byproduct alkali salt was demonstrated in a heated graphite reactor. The process was scaled up to reduce heat losses and to produce larger samples of silicon. Reagent delivery systems, scaled by a factor of 25, were built and operated at a production rate of 0.5 kg Si/h. Very rapid reactor heating rates are observed with wall temperatures reaching greater than 2000 K. Heat release parameters were measured using a cooled stainless steel reactor tube. A new reactor was designed.

  19. Optical properties and electronic structure of alkali doped SWNT

    NASA Astrophysics Data System (ADS)

    Nemes, Norbert M.; Fischer, John E.; Kamarás, Katalin; Borondics, Ferenc; Tanner, David B.; Rinzler, Andrew G.

    2003-03-01

    Alkali doped SWNT exhibit colors similar to alkali doped graphite (GIC). We study their electronic structure with IR reflectivity; the alkali dopants donate their valence electron to the SWNT host, so the free carrier concentration increases, shifting the Drude-edge into the visible spectral range. This is accompanied by a large shift of the Fermi-level, so the characteristic transitions between the 1D van Hove singularities of the undoped SWNT diminish. The presence of the alkali ions around the SWNT breaks the translational symmetry and increases coupling between parallel tubes within ropes. The momentum relaxation time shortens as the ropes become more three dimensional; alkali disorder contributes to the scattering. In p-type, HNO3 doped SWNT, the charge transfer is smaller; only the first subband of the semiconducting tubes gets depleted, shown by the disappearance of the first van Hove transition. This indicates a Fermi-level shift of ˜0.3 eV. The reflectivity has structure at low energy, which moves the Drude-peak to a sharp, intense peak at 0.1 eV in the optical conductivity, reminiscent of quasi-1D TTF-TCNQ.

  20. Chemistry of alkali cation exchanged faujasite and mesoporous NaX using alkyl halides and phosphates

    NASA Astrophysics Data System (ADS)

    Lee, Min-Hong

    The purpose of this work was to increase the reactivity of Faujasite X (NaX) zeolite toward the reactive decontamination of materials subject to nucleophilic attack by means of zeolite cation optimization and by means of the synthesis of mesoporous Faujasite X. Primary alkyl halides and trialkyl phosphates have been the test materials on which the cation-optimized and mesoporous zeolites have been tested. In the alkali cation optimization work, reactions of methyl iodide and 1-chloropropane with alkali metal cation exchanged Faujasite zeolite X were investigated at room temperature. The reactivity of the framework and the product formation were shown to depend on zeolite framework counter-cation. A quantitative study of zeolite product formation has been carried out, primarily using solid-state NMR spectroscopy. Large alkali cations showed preference toward substitution chemistry. In contrast, alkyl halide exposed LiX and NaX zeolites underwent both substitution and elimination. Subsequently introduced water molecules led to hydrolysis of framework species that was sensitive to framework counter-cation. The mesoporous NaX zeolites work undertakes to test whether an improvement in surface chemical reactivity can be achieved by introducing mesopores into the already reactive nucleophilic microporous NaX zeolite. Incorporation of the polydiallyl dimethyl ammonium chloride (PDADMAC) template and the formation of mesopores in Faujasite X zeolite (NaX) were successful and well-characterized. The mesopores are proposed to have occurred from incorporation of the cationic PDADMAC polymer into the zeolite by compensating zeolite framework charge. Subsequent sodium cation exchange of calcined mesoporous NaX was shown to restore the chemical reactivity characteristic of as-synthesized NaX. Trialkyl organophosphorous compounds underwent substitution reactions. The reactivity of both microporous and mesoporous Faujasite zeolite X and the product formation was shown to depend on

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

    DOEpatents

    Jackovitz, John F.; Pantier, Earl A.

    1982-05-18

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

  2. Alkali-Doped Lithium Orthosilicate Sorbents for Carbon Dioxide Capture.

    PubMed

    Yang, Xinwei; Liu, Wenqiang; Sun, Jian; Hu, Yingchao; Wang, Wenyu; Chen, Hongqiang; Zhang, Yang; Li, Xian; Xu, Minghou

    2016-09-01

    New alkali-doped (Na2 CO3 and K2 CO3 ) Li4 SiO4 sorbents with excellent performance at low CO2 concentrations were synthesized. We speculate that alkali doping breaks the orderly arrangement of the Li4 SiO4 crystals, hence increasing its specific surface area and the number of pores. It was shown that 10 wt % Na2 CO3 and 5 wt % K2 CO3 are the optimal additive ratios for doped sorbents to attain the highest conversions. Moreover, under 15 vol % CO2 , the doped sorbents present clearly faster absorption rates and exhibit stable cyclic durability with impressive conversions of about 90 %, at least 20 % higher than that of non-doped Li4 SiO4 . The attained conversions are also 10 % higher than the reported highest conversion of 80 % on doped Li4 SiO4 . The performance of Li4 SiO4 is believed to be enhanced by the eutectic melt, and it is the first time that the existence of eutectic Li/Na or Li/K carbonate on doped sorbents when absorbing CO2 at high temperature is confirmed; this was done using systematical analysis combining differential scanning calorimetry with in situ powder X-ray diffraction. PMID:27531239

  3. Transport properties of alkali metal doped fullerides

    SciTech Connect

    Yadav, Daluram Yadav, Nishchhal

    2015-07-31

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

  4. Transport properties of alkali metal doped fullerides

    NASA Astrophysics Data System (ADS)

    Yadav, Daluram; Yadav, Nishchhal

    2015-07-01

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

  5. Physics of solid and liquid alkali halide surfaces near the melting point

    NASA Astrophysics Data System (ADS)

    Zykova-Timan, T.; Ceresoli, D.; Tartaglino, U.; Tosatti, E.

    2005-10-01

    This paper presents a broad theoretical and simulation study of the high-temperature behavior of crystalline alkali halide surfaces typified by NaCl(100), of the liquid NaCl surface near freezing, and of the very unusual partial wetting of the solid surface by the melt. Simulations are conducted using two-body rigid-ion Born-Mayer-Huggins-Fumi-Tosi (BMHFT) potentials, with full treatment of long-range Coulomb forces. After a preliminary check of the description of bulk NaCl provided by these potentials, which seems generally good even at the melting point, we carry out a new investigation of solid and liquid surfaces. Solid NaCl(100) is found in this model to be very anharmonic and yet exceptionally stable when hot. It is predicted by a thermodynamic integration calculation of the surface free energy that NaCl(100) should be a well-ordered, nonmelting surface, metastable even well above the melting point. By contrast, the simulated liquid NaCl surface is found to exhibit large thermal fluctuations and no layering order. In spite of that, it is shown to possess a relatively large surface free energy. The latter is traced to a surface entropy deficit, reflecting some kind of surface short-range order. We show that the surface short-range order is most likely caused by the continuous transition of the bulk ionic melt into the vapor, made of NaCl molecules and dimers rather than of single ions. Finally, the solid-liquid interface free energy is derived through Young's equation from direct simulation of partial wetting of NaCl(100) by a liquid droplet. The resulting interface free energy is large, in line with the conspicuous solid-liquid 27% density difference. A partial wetting angle near 50° close to the experimental value of 48° is obtained in the process. It is concluded that three elements, namely, the exceptional anharmonic stability of the solid (100) surface, the molecular short-range order at the liquid surface, and the costly solid-liquid interface, all

  6. Excess-electron and excess-hole states of charged alkali halide clusters

    NASA Astrophysics Data System (ADS)

    Honea, Eric C.; Homer, Margie L.; Whetten, R. L.

    1990-12-01

    Charged alkali halide clusters from a He-cooled laser vaporization source have been used to investigate two distinct cluster states corresponding to the excess-electron and excess-hole states of the crystal. The production method is UV-laser vaporization of an alkali metal rod into a halogen-containing He flow stream, resulting in variable cluster composition and cooling sufficient to stabilize weakly bound forms. Detection of charged clusters is accomplished without subsequent ionization by pulsed-field time-of-flight mass spectrometry of the skimmed cluster beam. Three types of positively charged sodium fluoride cluster are observed, each corresponding to a distinct physical situation: NanF+n-1 (purely ionic form), Nann+1F+n-1 (excess-electron form), and NanF+n (excess-hole form). The purely ionic clusters exhibit an abundance pattern similar to that observed in sputtering and fragmentation experiments and are explained by the stability of completed cubic microlattice structures. The excess-electron clusters, in contrast, exhibit very strong abundance maxima at n = 13 and 22, corresponding to the all-odd series (2n + 1 = jxkxl;j,k,l odd). Their high relative stability is explained by the ease of Na(0) loss except when the excess electron localizes in a lattice site to complete a cuboid structure. These may correspond to the internal F-center state predicted earlier. A localized electron model incorporating structural simulation results as account for the observed pattern. The excess-hole clusters, which had been proposed as intermediates in the ionization-induced fragmentation of neutral AHCs, exhibit a smaller variation in stability, indicating that the hole might not be well localized.

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

    NASA Technical Reports Server (NTRS)

    Olson, D. B.; Miller, W. J.; Gould, R. K.

    1980-01-01

    The feasibility of using continuous high-temperature reactions of alkali metals and silicon halides to produce silicon in large quantities and of suitable purity for use in the production of photovoltaic solar cells was demonstrated. Low pressure experiments were performed demonstrating the production of free silicon and providing experience with the construction of reactant vapor generators. Further experiments at higher reagent flow rates were performed in a low temperature flow tube configuration with co-axial injection of reagents and relatively pure silicon was produced. A high temperature graphite flow tube was built and continuous separation of Si from NaCl was demonstrated. A larger scaled well stirred reactor was built. Experiments were performed to investigate the compatability of graphite based reactor materials of construction with sodium. At 1100 to 1200 K none of these materials were found to be suitable. At 1700 K the graphites performed well with little damage except to coatings of pyrolytic graphite and silicon carbide which were damaged.

  8. Physics of solid and liquid alkali halide surfaces near the melting point

    NASA Astrophysics Data System (ADS)

    Zykova-Timan, Tatyana; Ceresoli, Davide; Tartaglino, Ugo; Tosatti, Erio

    2006-03-01

    NaCl (and other alkali halide) crystal surfaces have the peculiar property of repelling their own melt. As a result they let themselves be wetted only partially by their own liquid at the melting point TM. We recently investigated the physical reasons for this unusual behavior. We found them through theory and molecular dynamics simulation to stem from the conspiracy of three factors. First, the solid NaCl(100) surface is exceptionally anharmonic,but also exceptionally stable. It can in fact survive even well above the melting point, for unlike most other surfaces it does not spontaneously melt. Second, the solid-liquid interface is very costly, due to a 27% density difference between solid and liquid. Third, the surface tension of liquid NaCl is relatively high. This last feature is due to an unexpected entropy deficit, that can in turn be traced to incipient molecular charge order in the outermost regions of the molten salt surface[1,2].[1] T. Zykova-Timan, D. Ceresoli, U. Tartaglino, E. Tosatti, Phys. Rev. Lett. 94, 176105 (2005) [2] T. Zykova-Timan, D. Ceresoli, U. Tartaglino, E. Tosatti, J. Chem. Phys. 123, 164701 (2005)

  9. UV laser-induced desorption mechanism analyzed through two-layer alkali halide samples.

    PubMed

    Fernández-Lima, F A; Ponciano, C R; da Silveira, E F

    2008-05-01

    Time of flight-mass spectrometry (TOF-MS) is used to analyze positive and negative desorbed ions generated by UV laser ablation of several alkali (X) halide (Y) salts. Most of the observed desorbed cluster ions have the structure (XY)(n)X(+) or (XY)(n)Y(-). Their desorption yields decrease as exp(-kn), where k approximately 2 for both series, suggesting that the neutral component (XY)(n) plays the dominant role in the desorption process. Mass spectrum measurements were performed for compound samples in which two salts (out of CsI, RbI, KBr, KCl and KI) are homogeneously mixed or disposed in two superposed layers. The detection of small new ion species and large cluster ions of the original salts supports the scenario that the uppermost layers are completely atomized while deep layers are emitted colder and fragmented: It is proposed that ns-pulsed laser induced desorption of ionic salts occurs via two sequential mechanisms: (1) ejection of cations and anions in the hot plume, followed by recombination into new cluster ions and (2) ejection of relatively cold preformed species originated from deep layers or from periphery of the irradiated region. PMID:18095386

  10. Dynamics of nuclear wave packets at the F center in alkali halides

    NASA Astrophysics Data System (ADS)

    Koyama, Takeshi; Suemoto, Tohru

    2011-07-01

    The F center in alkali halides is a well-known prototype of a strongly coupled localized electron-phonon system. This colour center is one of the long studied targets in the field of photophysics because it is simple but rich in variety. Steady-state spectroscopy, such as modulation spectroscopy and Raman scattering spectroscopy, has elucidated the strength of the electron-phonon coupling in the (meta-)stable state, i.e. the ground state and the relaxed excited state. Picosecond spectroscopy has improved understanding of the state mixing in the transient state. Owing to recent developments of ultrafast lasers with pulse widths shorter than oscillation periods of phonons, it has been possible to perform real-time observation of lattice vibration, and the understanding of the transient state has been remarkably expanded. In this paper, we review early and present studies on dynamics of electron-phonon coupling at the F center, especially recent real-time observations on the dynamics of nuclear wave packets in the excited state of the F center in KI, KBr, KCl and RbCl. These real-time observations reveal (i) spatial extension of the electronic wave function of a trapped electron, (ii) the difference between the coupled phonons in the ground state and the excited state, (iii) diabatic transition between the adiabatic potential energy surfaces and (iv) anharmonicity of the potential energy surface.

  11. Surface Spectroscopy Studies of the Reactive Uptake of Ozone on Alkali Halides

    NASA Astrophysics Data System (ADS)

    Newberg, J. T.; Hemminger, J. C.

    2003-12-01

    Heterogeneous reactions in the atmosphere have attracted a lot of attention. In particular, reactions involving sea-salt in the form of aerosol droplets, particles, and/or sea-ice have been implicated to significantly affect the chemistry and composition of the marine boundary layer. For example, highly reactive chlorine and bromine atoms resulting from the oxidation of sea-salt halides (Cl- and Br-) have been implicated in tropospheric ozone depletion in the arctic and in lower latitude marine regions, as well as the deposition of mercury. While the heterogeneous processing of sea-salt has been studied extensively in laboratory, field and model studies, the mechanistic details behind the release of gas-phase halogens remains unclear and has sparked some interests. Recently there has been attention focused on the interaction of important atmospheric oxidants (e.g., OH and O3) with halides that reside at the air-particle interface of sea-salt. Such chemical interactions at the surface of particles may lead to unique chemical transformations that can alter current views of known chemical processing of sea-salt particles. There are several laboratory investigations which have investigated the surface reactivity of salts by measuring the reactive loss and/or formation of gas-phase species, indicating that reactions at the interface likely play an important role in aerosol chemistry. The efficacy of such surface-phase chemistry has yet to be elucidated with surface spectroscopy studies. X-ray photoelectron spectroscopy (XPS) is a surface spectroscopy technique with submonolayer resolution. Using XPS, we have investigated changes in the surface chemistry of various alkali halide salts upon exposure to ozone in an ultra-high vacuum (UHV) instrument. Salt samples were either freshly cleaved single crystals which were prepared from a melt, or purified salt crystals/powders pressed into pellets. Upon exposure to ozone, oxygen on the salt surfaces was monitored by measuring

  12. Optical properties of alkali halide crystals from all-electron hybrid TD-DFT calculations

    SciTech Connect

    Webster, R. Harrison, N. M.; Bernasconi, L.

    2015-06-07

    We present a study of the electronic and optical properties of a series of alkali halide crystals AX, with A = Li, Na, K, Rb and X = F, Cl, Br based on a recent implementation of hybrid-exchange time-dependent density functional theory (TD-DFT) (TD-B3LYP) in the all-electron Gaussian basis set code CRYSTAL. We examine, in particular, the impact of basis set size and quality on the prediction of the optical gap and exciton binding energy. The formation of bound excitons by photoexcitation is observed in all the studied systems and this is shown to be correlated to specific features of the Hartree-Fock exchange component of the TD-DFT response kernel. All computed optical gaps and exciton binding energies are however markedly below estimated experimental and, where available, 2-particle Green’s function (GW-Bethe-Salpeter equation, GW-BSE) values. We attribute this reduced exciton binding to the incorrect asymptotics of the B3LYP exchange correlation ground state functional and of the TD-B3LYP response kernel, which lead to a large underestimation of the Coulomb interaction between the excited electron and hole wavefunctions. Considering LiF as an example, we correlate the asymptotic behaviour of the TD-B3LYP kernel to the fraction of Fock exchange admixed in the ground state functional c{sub HF} and show that there exists one value of c{sub HF} (∼0.32) that reproduces at least semi-quantitatively the optical gap of this material.

  13. Simple electrolyte solutions: Comparison of DRISM and molecular dynamics results for alkali halide solutions

    PubMed Central

    Joung, In Suk; Luchko, Tyler; Case, David A.

    2013-01-01

    Using the dielectrically consistent reference interaction site model (DRISM) of molecular solvation, we have calculated structural and thermodynamic information of alkali-halide salts in aqueous solution, as a function of salt concentration. The impact of varying the closure relation used with DRISM is investigated using the partial series expansion of order-n (PSE-n) family of closures, which includes the commonly used hypernetted-chain equation (HNC) and Kovalenko-Hirata closures. Results are compared to explicit molecular dynamics (MD) simulations, using the same force fields, and to experiment. The mean activity coefficients of ions predicted by DRISM agree well with experimental values at concentrations below 0.5 m, especially when using the HNC closure. As individual ion activities (and the corresponding solvation free energies) are not known from experiment, only DRISM and MD results are directly compared and found to have reasonably good agreement. The activity of water directly estimated from DRISM is nearly consistent with values derived from the DRISM ion activities and the Gibbs-Duhem equation, but the changes in the computed pressure as a function of salt concentration dominate these comparisons. Good agreement with experiment is obtained if these pressure changes are ignored. Radial distribution functions of NaCl solution at three concentrations were compared between DRISM and MD simulations. DRISM shows comparable water distribution around the cation, but water structures around the anion deviate from the MD results; this may also be related to the high pressure of the system. Despite some problems, DRISM-PSE-n is an effective tool for investigating thermodynamic properties of simple electrolytes. PMID:23387564

  14. a Study of Two Electron Defect Systems in Alkali Halide Crystals

    NASA Astrophysics Data System (ADS)

    Zhang, Chang Gang

    1993-01-01

    The structures of two electron defect systems in alkali halide crystals are studied. The systems which have been studied include: two electrons localized at an anion vacancy (F^'-centre); positronium self-trapped at an anion vacancy (Fe ^+-centre); positron self-trapped at a cation vacancy (F_{rm anti} -centre); positronium self-trapped at an interstice; and positronium in a Bloch state. An improved version of the extended-ion method which is based on the one electron Hartree-Fock approximation is used to perform these calculations. Its main feature is the exclusive use of floating 1s Gaussian functions as basis. For the multi-electron defect systems, the calculation of matrix elements of two electron interaction terms is a most difficult problem. We developed an effective approach to treat this interaction approximately. The correlation effect of defect electrons is partly accounted for by properly arranged Gaussian basis. The binding energy, thermal dissociation energy, and transition energy between ground state and excited state are calculated for F ^'-centres. A defect model with negative-U properties was introduced to interpret the deeply bound F^'-centre. Calculations of positron binding energies are made for Fe^+ -centres and F_{rm anti }-centres. In addition, we evaluate the angular correlation and lifetime of an annihilated electron-positron pair for Fe^+-centres, localized positronium and Bloch state positronium. The observed phenomena such as the transition of positronium from Bloch state to localized state, and the crystallographic effect are examined theoretically. The calculated results regarding various properties of crystals are in reasonably good agreement with experiment.

  15. Exotic s-wave superconductivity in alkali-doped fullerides

    NASA Astrophysics Data System (ADS)

    Nomura, Yusuke; Sakai, Shiro; Capone, Massimo; Arita, Ryotaro

    2016-04-01

    Alkali-doped fullerides ({{A}3}{{\\text{C}}60} with A  =  K, Rb, Cs) show a surprising phase diagram, in which a high transition-temperature ({{T}\\text{c}} ) s-wave superconducting state emerges next to a Mott insulating phase as a function of the lattice spacing. This is in contrast with the common belief that Mott physics and phonon-driven s-wave superconductivity are incompatible, raising a fundamental question on the mechanism of the high-{{T}\\text{c}} superconductivity. This article reviews recent ab initio calculations, which have succeeded in reproducing comprehensively the experimental phase diagram with high accuracy and elucidated an unusual cooperation between the electron-phonon coupling and the electron-electron interactions leading to Mott localization to realize an unconventional s-wave superconductivity in the alkali-doped fullerides. A driving force behind the exotic physics is unusual intramolecular interactions, characterized by the coexistence of a strongly repulsive Coulomb interaction and a small effectively negative exchange interaction. This is realized by a subtle energy balance between the coupling with the Jahn-Teller phonons and Hund’s coupling within the {{\\text{C}}60} molecule. The unusual form of the interaction leads to a formation of pairs of up- and down-spin electrons on the molecules, which enables the s-wave pairing. The emergent superconductivity crucially relies on the presence of the Jahn-Teller phonons, but surprisingly benefits from the strong correlations because the correlations suppress the kinetic energy of the electrons and help the formation of the electron pairs, in agreement with previous model calculations. This confirms that the alkali-doped fullerides are a new type of unconventional superconductors, where the unusual synergy between the phonons and Coulomb interactions drives the high-{{T}\\text{c}} superconductivity.

  16. Exotic s-wave superconductivity in alkali-doped fullerides.

    PubMed

    Nomura, Yusuke; Sakai, Shiro; Capone, Massimo; Arita, Ryotaro

    2016-04-20

    Alkali-doped fullerides (A3C60 with A = K, Rb, Cs) show a surprising phase diagram, in which a high transition-temperature (Tc) s-wave superconducting state emerges next to a Mott insulating phase as a function of the lattice spacing. This is in contrast with the common belief that Mott physics and phonon-driven s-wave superconductivity are incompatible, raising a fundamental question on the mechanism of the high-Tc superconductivity. This article reviews recent ab initio calculations, which have succeeded in reproducing comprehensively the experimental phase diagram with high accuracy and elucidated an unusual cooperation between the electron-phonon coupling and the electron-electron interactions leading to Mott localization to realize an unconventional s-wave superconductivity in the alkali-doped fullerides. A driving force behind the exotic physics is unusual intramolecular interactions, characterized by the coexistence of a strongly repulsive Coulomb interaction and a small effectively negative exchange interaction. This is realized by a subtle energy balance between the coupling with the Jahn-Teller phonons and Hund's coupling within the C60 molecule. The unusual form of the interaction leads to a formation of pairs of up- and down-spin electrons on the molecules, which enables the s-wave pairing. The emergent superconductivity crucially relies on the presence of the Jahn-Teller phonons, but surprisingly benefits from the strong correlations because the correlations suppress the kinetic energy of the electrons and help the formation of the electron pairs, in agreement with previous model calculations. This confirms that the alkali-doped fullerides are a new type of unconventional superconductors, where the unusual synergy between the phonons and Coulomb interactions drives the high-Tc superconductivity. PMID:26974650

  17. Liquid madelung energy and schottky defect energy related to liquid structure and melting temperature for alkali halides

    SciTech Connect

    March, N.H.; Tosi, M.P.

    1985-01-01

    Motivated by the work of Reiss et al. in which the melting temperature T /SUB m/ of alkali halides is correlated with Coulomb energy, we consider the cohesive energy W of ionic melts and Schottky defect energy E /SUB s/ in the hot crystal, relative to the thermal energy k /SUB B/ T /SUB m/ . It is shown here that is accurately approximated by the liquid Madelung energy and hence that W/k /SUB B/ T /SUB m/ relates to the charge-charg direct correlation function c /SUB QQ/ (r) at r = 0. The existence of a ''Madelung constant'' for the liquid at T /SUB m/ is thereby demonstrated through the alkali halide series. An estimate of the ratio E /SUB s/ /k /SUB B/ T /SUB m/ i then considered; the basic additional ingredient being argued to be the static dielectric constant of the solid. Th BarrDawson-Lidiard empirical correlation between E /SUB s/ and k /SUB B/ T /SUB m/ can be understood in this way.

  18. Universal scaling of potential energy functions describing intermolecular interactions. II. The halide-water and alkali metal-water interactions

    SciTech Connect

    Werhahn, Jasper C.; Akase, Dai; Xantheas, Sotiris S.

    2014-08-14

    The scaled versions of the newly introduced [S. S. Xantheas and J. C. Werhahn, J. Chem. Phys.141, 064117 (2014)] generalized forms of some popular potential energy functions (PEFs) describing intermolecular interactions – Mie, Lennard-Jones, Morse, and Buckingham exponential-6 – have been used to fit the ab initio relaxed approach paths and fixed approach paths for the halide-water, X-(H2O), X = F, Cl, Br, I, and alkali metal-water, M+(H2O), M = Li, Na, K, Rb, Cs, interactions. The generalized forms of those PEFs have an additional parameter with respect to the original forms and produce fits to the ab initio data that are between one and two orders of magnitude better in the χ2 than the original PEFs. They were found to describe both the long-range, minimum and repulsive wall of the respective potential energy surfaces quite accurately. Overall the 4-parameter extended Morse (eM) and generalized Buckingham exponential-6 (gBe-6) potentials were found to best fit the ab initio data for these two classes of ion-water interactions. Finally, the fitted values of the parameter of the (eM) and (gBe-6) PEFs that control the repulsive wall of the potential correlate remarkably well with the ionic radii of the halide and alkali metal ions.

  19. Low-Energy Grazing Ion-Scattering from Alkali-Halide Surfaces: A Novel Approach to C-14 Detection

    SciTech Connect

    Meyer, Fred W; Galutschek, Ernst; Hotchkis, Michael

    2009-01-01

    Carbon-14 labeled compounds are widely used in the pharmaceutical industry, e.g., as tracers to determine the fate of these compounds in vivo. Conventional accelerator mass spectrometry (AMS) is one approach that offers sufficiently high sensitivity to avoid radiological waste and contamination issues in such studies, but requires large, expensive facilities that are usually not solely dedicated to this task. At the ORNL Multicharged Ion Research Facility (MIRF) we are exploring a small size, low cost alternative to AMS for biomedical 14C tracer studies that utilizes ECR-ion-source-generated keV-energy-range multicharged C beams grazingly incident on an alkali halide target, where efficient negative ion production by multiple electron capture takes place. By using C ion charge states of +3 or higher, the molecular isobar interference at mass 14, e.g. 12CH2 and 13CH, is eliminated. The negatively charged ions in the beam scattered from the alkali halide surface are separated from other scattered charge states by two large acceptance ({approx}15 msr) stages of electrostatic analysis. The N-14 isobar interference is thus removed, since N does not support a stable negative ion. Initial results for C-14 detection obtained using C-14 enriched CO2 from ANSTO will be described.

  20. Integrating 2-D position sensitive X-ray detectors with low-density alkali halide storage targets

    NASA Astrophysics Data System (ADS)

    Haubold, H.-G.; Hoheisel, W.; Hiller, P.

    1986-05-01

    For the use in scattering experiments with synchrotron radiation, integrating position sensitive X-ray detectors are discussed. These detectors store the photon number equivalent charge (PNEC) in low-density alkali halide targets. Performance tests are given for a detector which uses a Gd 2O 2S fluorescence screen for X-ray detection and the low-density KCl storage target of a television SEC vidicon tube for photon integration. Rather than directly by X-rays, this target is charged by 6 keV electrons from the image intensifier section of the vidicon. Its excellent storage capability allows measurements of extremely high-contrast, high-flux X-ray patterns with the same accuracy as achieved with any single photon detection system if the discussed readout techniques are applied.

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

    NASA Technical Reports Server (NTRS)

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

    1981-01-01

    High temperature reactions of silicon halides with alkali metals for the production of solar grade silicon are described. Product separation and collection processes were evaluated, measure heat release parameters for scaling purposes and effects of reactants and/or products on materials of reactor construction were determined, and preliminary engineering and economic analysis of a scaled up process were made. The feasibility of the basic process to make and collect silicon was demonstrated. The jet impaction/separation process was demonstrated to be a purification process. The rate at which gas phase species from silicon particle precursors, the time required for silane decomposition to produce particles, and the competing rate of growth of silicon seed particles injected into a decomposing silane environment were determined. The extent of silane decomposition as a function of residence time, temperature, and pressure was measured by infrared absorption spectroscopy. A simplistic model is presented to explain the growth of silicon in a decomposing silane enviroment.

  2. Size distributions and geometries of alkali halide nanoclusters probed using ESI FT-ICR mass spectrometry and quantum chemistry

    NASA Astrophysics Data System (ADS)

    Lemke, K.; Sadjadi, S.; Seward, T.

    2010-12-01

    The structures and energetic properties of ionic alkali metal halide clusters play a significant role in our understanding of aqueous geochemical processes such as salt dissolution, precipitation and neutralization reactions. Mass spectrometric and quantum chemical studies of such systems offer new opportunities to study the size-dependent evolution of cluster structures, the occurrence of magic number species as well as their fundamental properties. The work here presents new results for the stability, abundance and structure of pure [Na(NaClm)]+ , [K(KCl)m]+ and mixed [Na(NaCl)p(KCl)q]+ metal halide clusters with m<23 and p+q<14, respectively, using ultra-high resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR/MS) in combination with the Gn and CBS-x multistep ab initio methods. Ion-cluster experiments were conducted on a modified 7T Bruker FT-ICR/MS equipped with electrospray ionization (ESI) sources and a custom-designed solvent gas inlet interface. In ESI FT-ICR/MS experiments performed with solutions containing NaCl and KCl salts (1mM; 80/20 CH3CN/H2O), singly and doubly charged salt clusters were generated up to a cluster size of [Na(NaCl)22]+, [K(KCl)17]+ and [K2(KCl)21,23]2+, respectively, including “magic number” clusters that correspond to the completed cluster cuboids with the dimensions 3x3x1 (m=4), 3x3x2+3 (m=10) 3x3x3 (m=13) and 3x3x5 (m=22) (see Figure). On the other hand, no pure clusters except [K(KCl)1-3]+ were generated when alkali halides were electrosprayed from 1mM NaCl/KCl solutions. Instead, mixed [Na(NaCl)p(KCl)q]+ clusters are generated up to p+q=14, which are the largest mixed alkali halide clusters yet generated in mass spectrometric experiments, including a suite of ionic species that are generated via CH3CN fragmentation and charge transfer in [Na(CH3CN)n]+ to yield the clusters [Na(NaCN)(CH3CN)n-1]+. We describe our ESI FT-ICR/MS experiments and discuss ion cluster abundances and extent of clustering

  3. Ultrabroad Photoluminescence and Electroluminescence at New Wavelengths from Doped Organometal Halide Perovskites.

    PubMed

    Zhou, Yang; Yong, Zi-Jun; Zhang, Kai-Cheng; Liu, Bo-Mei; Wang, Zhao-Wei; Hou, Jing-Shan; Fang, Yong-Zheng; Zhou, Yi; Sun, Hong-Tao; Song, Bo

    2016-07-21

    Doping of semiconductors by introducing foreign atoms enables their widespread applications in microelectronics and optoelectronics. We show that this strategy can be applied to direct bandgap lead-halide perovskites, leading to the realization of ultrawide photoluminescence (PL) at new wavelengths enabled by doping bismuth (Bi) into lead-halide perovskites. Structural and photophysical characterization reveals that the PL stems from one class of Bi doping-induced optically active center, which is attributed to distorted [PbI6] units coupled with spatially localized bipolarons. Additionally, we find that compositional engineering of these semiconductors can be employed as an additional way to rationally tune the PL properties of doped perovskites. Finally, we accomplished the electroluminescence at cryogenic temperatures by using this system as an emissive layer, marking the first electrically driven devices using Bi-doped photonic materials. Our results suggest that low-cost, earth-abundant, solution-processable Bi-doped perovskite semiconductors could be promising candidate materials for developing optical sources operating at new wavelengths. PMID:27377481

  4. Yb-doped large-mode-area laser fiber fabricated by halide-gas-phase-doping technique

    NASA Astrophysics Data System (ADS)

    Peng, Kun; Wang, Yuying; Ni, Li; Wang, Zhen; Gao, Cong; Zhan, Huan; Wang, Jianjun; Jing, Feng; Lin, Aoxiang

    2015-06-01

    In this manuscript, we designed a rare-earth-halide gas-phase-doping setup to fabricate a large-mode-area fiber for high power laser applications. YbCl3 and AlCl3 halides are evaporated, carried respectively and finally mixed with usual host gas material SiCl4 at the hot zone of MCVD system. Owing to the all-gas-phasing reaction process and environment, the home-made Yb-doped fiber preform has a homogeneous large core and modulated refractive index profile to keep high beam quality. The drawn fiber core has a small numerical aperture of 0.07 and high Yb concentration of 9500 ppm. By using a master oscillator power amplifier system, nearly kW-level (951 W) laser output power was obtained with a slope efficiency of 83.3% at 1063.8 nm, indicating the competition and potential of the halide-gas-phase-doping technique for high power laser fiber fabrication.

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

    NASA Astrophysics Data System (ADS)

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

    1992-11-01

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

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

    PubMed

    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. PMID:27264676

  7. Low-frequency modes of aqueous alkali halide solutions: an ultrafast optical Kerr effect study.

    PubMed

    Heisler, Ismael A; Mazur, Kamila; Meech, Stephen R

    2011-03-01

    A detailed picture of aqueous solvation of ions is central to the understanding of diverse phenomena in chemistry and biology. In this work, we report polarization resolved THz time domain measurements of the Raman spectral density of a wide range of aqueous salt solutions. In particular, the isotropic Raman spectral density reveals the frequency of the hydrogen bond formed between the halide ion and water. The frequency of this mode is measured for the series Cl(-), Br(-), and I(-) as a function of concentration, cation size, and charge. The frequencies extrapolated to zero concentration permit an estimation of the force constant of the mode, which is found to decrease with increasing halide mass and to be similar to the force constant associated with the water-water hydrogen bond. This result is consistent with recent calculations. The extrapolation of the frequency of the chloride hydrogen bond to zero concentration reveals a dependence of the frequency on the nature of the cation. This is ascribed to an interaction between the solvated anion and cation even at the lowest concentration studied here (<0.15 M). It is suggested that this behavior reflects the influence of the electric field of the cation on the hydrogen bond of an adjacent anion. Such interactions should be taken into account when modeling experimental data recorded at concentrations of ions in excess of 0.1 M. These measurements of the isotropic Raman spectral density are compared with those for the anisotropic response, which reflects the frequencies of the full range of hydrogen bonds in aqueous salt solutions. The anisotropic spectral density recovered can be modeled in terms of a concentration-dependent population of water-water H-bonds with a frequency unaffected by the ions, the halide-water hydrogen bonds, and a low-frequency collision-induced contribution. PMID:21291185

  8. Spectroscopic investigations of Nd(3+)-doped alkali chloroborophosphate glasses.

    PubMed

    Moorthy, L R; Rao, T S; Jayasimhadri, M; Radhapathy, A; Murthy, D V R

    2004-09-01

    Optical absorption spectra were studied in wavelength region 400-900 nm for the Nd(3+)-doped alkali (R = Li, Na and K) chloroborophosphate glasses at room temperature. The energy level scheme of the 4f(3) electron configuration was deduced from the observed energy level data using a parametrized Hamiltonian (H(F1)) model which includes 20 free-ion interaction parameters. Reasonable correlation was obtained between the experimental and calculated energy levels. The Judd-Ofelt model for the intensity analysis of induced electric dipole transitions has been applied to the measured oscillator strengths of the absorption bands to determine the three phenomenological intensity parameters Omega(2), Omega(4) and Omega(6) for each glass. Using these parameters, the total radiative transition rates (A(T)), non-radiative relaxation rates (W(NR)), branching ratios (beta(R)), integrated cross-sections for the stimulated emission (Sigma), excited state emission intensities (f(ESE)) and excited state absorption intensities (f(ESA)) have been theoretically calculated for certain excited Nd(3+) fluorescent levels. From the results obtained, the conclusion is made about the possibility of using these glasses as laser media. PMID:15294227

  9. EPR study of electron bombarded alkali- and alkaline-earth halide crystal surfaces

    NASA Technical Reports Server (NTRS)

    Fryburg, G. C.; Lad, R. A.

    1975-01-01

    An EPR study of electron bombarded LiF, NaCl, KCl, CaF2 and BaF2 polycrystalline surfaces has shown that small metal particles are formed on the surfaces of the crystals. Identification was made from CESR signals. The symmetric line-shape of the signals, even at 77 K, indicated that the particles were less than 0.5 micron in diameter. Signals due to F centers were observed in LiF but not in the other halides. Implications to metal deposition are considered.

  10. Lattice model calculation of elastic and thermodynamic properties at high pressure and temperature. [for alkali halides in NaCl lattice

    NASA Technical Reports Server (NTRS)

    Demarest, H. H., Jr.

    1972-01-01

    The elastic constants and the entire frequency spectrum were calculated up to high pressure for the alkali halides in the NaCl lattice, based on an assumed functional form of the inter-atomic potential. The quasiharmonic approximation is used to calculate the vibrational contribution to the pressure and the elastic constants at arbitrary temperature. By explicitly accounting for the effect of thermal and zero point motion, the adjustable parameters in the potential are determined to a high degree of accuracy from the elastic constants and their pressure derivatives measured at zero pressure. The calculated Gruneisen parameter, the elastic constants and their pressure derivatives are in good agreement with experimental results up to about 600 K. The model predicts that for some alkali halides the Grunesen parameter may decrease monotonically with pressure, while for others it may increase with pressure, after an initial decrease.

  11. Ca-Fe and Alkali-Halide Alteration of an Allende Type B CAI: Aqueous Alteration in Nebular or Asteroidal Settings

    NASA Technical Reports Server (NTRS)

    Ross, D. K.; Simon, J. I.; Simon, S. B.; Grossman, L.

    2012-01-01

    Ca-Fe and alkali-halide alteration of CAIs is often attributed to aqueous alteration by fluids circulating on asteroidal parent bodies after the various chondritic components have been assembled, although debate continues about the roles of asteroidal vs. nebular modification processes [1-7]. Here we report de-tailed observations of alteration products in a large Type B2 CAI, TS4 from Allende, one of the oxidized subgroup of CV3s, and propose a speculative model for aqueous alteration of CAIs in a nebular setting. Ca-Fe alteration in this CAI consists predominantly of end-member hedenbergite, end-member andradite, and compositionally variable, magnesian high-Ca pyroxene. These phases are strongly concentrated in an unusual "nodule" enclosed within the interior of the CAI (Fig. 1). The Ca, Fe-rich nodule superficially resembles a clast that pre-dated and was engulfed by the CAI, but closer inspection shows that relic spinel grains are enclosed in the nodule, and corroded CAI primary phases interfinger with the Fe-rich phases at the nodule s margins. This CAI also contains abundant sodalite and nepheline (alkali-halide) alteration that occurs around the rims of the CAI, but also penetrates more deeply into the CAI. The two types of alteration (Ca-Fe and alkali-halide) are adjacent, and very fine-grained Fe-rich phases are associated with sodalite-rich regions. Both types of alteration appear to be replacive; if that is true, it would require substantial introduction of Fe, and transport of elements (Ti, Al and Mg) out of the nodule, and introduction of Na and Cl into alkali-halide rich zones. Parts of the CAI have been extensively metasomatized.

  12. Polybenzimidazole membranes for direct methanol fuel cell: Acid-doped or alkali-doped?

    NASA Astrophysics Data System (ADS)

    Li, Long-Yun; Yu, Bor-Chern; Shih, Chao-Ming; Lue, Shingjiang Jessie

    2015-08-01

    Polybenzimidazole (PBI) films immersed in 2 M phosphoric acid (H3PO4) or 6 M potassium hydroxide (KOH) solution form electrolytes for conducting proton or hydroxide, respectively. A direct methanol fuel cell (DMFC) with the alkali-KOH doped PBI gives 117.9 mW cm-2 of power output which is more than 2 times greater than the power density of 46.5 mW cm-2 with the H3PO4-doped PBI (vs.) when both of the DMFCs use a micro porous layer (MPL) in a gas-fed cathode and a MPL-free anode and are operated at 90 °C. When the MPL-free anode and cathode are used and the fuel flow rate is tripled, the peak power density of alkaline DMFC reaches 158.9 mW cm-2.

  13. Interaction of wide band gap single crystals with 248 nm excimer laser radiation. XII. The emission of negative atomic ions from alkali halides

    SciTech Connect

    Kimura, Kenichi; Langford, S. C.; Dickinson, J. T.

    2007-12-01

    Many wide band gap materials yield charged and neutral emissions when exposed to sub-band-gap laser radiation at power densities below the threshold for optical breakdown and plume formation. In this work, we report the observation of negative alkali ions from several alkali halides under comparable conditions. We observe no evidence for negative halogen ions, in spite of the high electron affinities of the halogens. Significantly, the positive and negative alkali ions show a high degree of spatial and temporal overlap. A detailed study of all the relevant particle emissions from potassium chloride (KCl) suggests that K{sup -} is formed by the sequential attachment of two electrons to K{sup +}.

  14. Shallow electron traps in alkali halide crystals: Mollwo-Ivey relations of the optical absorption bands

    NASA Astrophysics Data System (ADS)

    Ziraps, Valters

    2001-03-01

    Evidences are given that two classes of the transient IR- absorption bands: (a) with max. at 0.27-0.36 eV in NaCl, KCl, KBr, KI and RbCl (due to shallow electron traps according G. Jacobs or due to bound polarons according E.V. Korovkin and T.A. Lebedkina) and (b) with max. at 0.15-0.36 eV in NaI, NaBr, NaCl:I, KCl:I, RbCl:I and RbBr:I (due to on-center STE localized at iodine dimer according M. Hirai and collaborators) are caused by the same defect- atomic alkali impurity center [M+]c0e- (electron e- trapped by a substitutional smaller size alkali cation impurity [M+]c0). The Mollwo-Ivey plots (for the transient IR-absorption bands) of the zero-phonon line energy E0 (for NaCl, KCl, KBr, RbCl and NaBr, KCl:I) and/or the low-energy edge valued E0 (for NaI, RbCl:I, RbBr:I) versus anion-cation distance (d) evidence that two types of the [M+]c0e- centers are predominant: (a) [Na+]c0e- in the KX and RbX host crystals with the relation E0approximately equals 6.15/d2.74, (b) [Li+]c03- in the NaX host crystals - E0approximately equals 29.4/d4.72. The Mollwo-Ivey relation E0approximately equals 18.36/d(superscript 2.70 is fulfilled as well for the F' band in NaCl, KCl, KBr, KI, RbCl, RbI if we use the F' center optical binding energy values E0.

  15. Structural and electronic properties of alkali-doped single-walled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Nemes, Norbert Marcel

    In this thesis, we study the properties of alkali doped single walled carbon nanotubes (SWNT). SWNT are crystallized into ropes, which display the one-dimensional electronic properties of the constituent nanotubes. Using x-ray diffraction, we show that the alkali atoms invade the channels in the triangular rope lattice and determine the structure of the doped ropes. We show that the diffraction profile of the doped SWNT is best described by a model where the alkali ions surround each tube in an ordered fashion by dilating the channels. Alkali doped SWNT exhibit colors similar to alkali doped graphite (GIC). We study their electronic structure with IR reflectivity; the alkali dopants donate their valence electron to the SWNT host, so the free carrier concentration increases, shifting the Drude-edge into the visible spectral range. This is accompanied by a large shift of the Fermi-level, so the characteristic transitions between the 1D van Hove singularities of the undoped SWNT diminish. The presence of the alkali ions around the SWNT breaks the translational symmetry and increases coupling between parallel tubes within ropes. We find that the momentum relaxation time shortens as the ropes become more three dimensional. We also find that alkali disorder contributes to the scattering. In p-type, HNO3 doped SWNT, the charge transfer is smaller; only the first subband of the semiconducting tubes gets depleted, shown by the disappearance of the first van Hove transition. This indicates a Fermi-level shift of ˜0.3 eV. The reflectivity has structure at low energy, which moves the Drude-peak to a sharp, intense peak at 0.1 eV in the optical conductivity, reminiscent of quasi-1D TTF-TCNQ. The DC conductivity also increases ˜80-fold during doping. The low temperature divergence of undoped SWNT disappears in alkali doped SWNT. However, we find that oxygen can modulate the low-T divergence. After outgassing, the divergence becomes ˜10 times stronger. We interpret the low

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

  17. Well-ordered monolayers of alkali-doped coronene and picene: Molecular arrangements and electronic structures

    SciTech Connect

    Yano, M.; Endo, M.; Hasegawa, Y.; Okada, R.; Yamada, Y. Sasaki, M.

    2014-07-21

    Adsorptions of alkali metals (such as K and Li) on monolayers of coronene and picene realize the formation of ordered phases, which serve as well-defined model systems for metal-intercalated aromatic superconductors. Upon alkali-doping of the monolayers of coronene and picene, scanning tunneling microscopy and X-ray absorption spectroscopy revealed the rearrangement of the entire molecular layer. The K-induced reconstruction of both monolayers resulted in the formation of a structure with a herringbone-like arrangement of molecules, suggesting the intercalation of alkali metals between molecular planes. Upon reconstruction, a shift in both the vacuum level and core levels of coronene was observed as a result of a charge transfer from alkali metals to coronene. In addition, a new density of states near the Fermi level was formed in both the doped coronene and the doped picene monolayers. This characteristic electronic feature of the ordered monolayer has been also reported in the multilayer picene films, ensuring that the present monolayer can model the properties of the metal-intercalated aromatic hydrocarbons. It is suggested that the electronic structure near the Fermi level is sensitive to the molecular arrangement, and that both the strict control and determinations of the molecular structure in the doped phase should be important for the determination of the electronic structure of these materials.

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

    NASA Astrophysics Data System (ADS)

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

    1991-05-01

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

  19. Evaluation of the physi- and chemisorption of hydrogen in alkali (Na, Li) doped fullerenes

    SciTech Connect

    Ward, Patrick A.; Teprovich, Jr., Jospeph A.; Compton, Robert N.; Schwartz, Viviane; Veith, Gabriel M.; Zidan, Ragiay

    2015-01-11

    Here, alkali doped fullerenes synthesized by two different solvent assisted mixing techniques are compared for their hydrogen uptake activity. In this study we investigated the interaction of hydrogen with alkali doped fullerenes via physisorption. In addition, we present the first mass spectrometric evidence for the formation of C60H60 via chemisorption. Hydrogen physisorption isotherms up to 1 atm at temperatures ranging from 77-303 K were measured demonstrating an increase in hydrogen uptake versus pure C60 and increased isosteric heats of adsorption for the lithium doped fullerene Li12C60. However, despite these improvements the low amount of physisorbed hydrogen at 1 atm and 77 K in these materials suggests that fullerenes do not possess enough accessible surface area to effectively store hydrogen due to their close packed crystalline nature.

  20. Evaluation of the physi- and chemisorption of hydrogen in alkali (Na, Li) doped fullerenes

    DOE PAGESBeta

    Ward, Patrick A.; Teprovich, Jr., Jospeph A.; Compton, Robert N.; Schwartz, Viviane; Veith, Gabriel M.; Zidan, Ragiay

    2015-01-11

    Here, alkali doped fullerenes synthesized by two different solvent assisted mixing techniques are compared for their hydrogen uptake activity. In this study we investigated the interaction of hydrogen with alkali doped fullerenes via physisorption. In addition, we present the first mass spectrometric evidence for the formation of C60H60 via chemisorption. Hydrogen physisorption isotherms up to 1 atm at temperatures ranging from 77-303 K were measured demonstrating an increase in hydrogen uptake versus pure C60 and increased isosteric heats of adsorption for the lithium doped fullerene Li12C60. However, despite these improvements the low amount of physisorbed hydrogen at 1 atm andmore » 77 K in these materials suggests that fullerenes do not possess enough accessible surface area to effectively store hydrogen due to their close packed crystalline nature.« less

  1. Temperature-dependent solubilities and mean ionic activity coefficients of alkali halides in water from molecular dynamics simulations.

    PubMed

    Mester, Zoltan; Panagiotopoulos, Athanassios Z

    2015-07-28

    The mean ionic activity coefficients of aqueous KCl, NaF, NaI, and NaCl solutions of varying concentrations have been obtained from molecular dynamics simulations following a recently developed methodology based on gradual insertions of salt molecules [Z. Mester and A. Z. Panagiotopoulos, J. Chem. Phys. 142, 044507 (2015)]. The non-polarizable ion models of Weerasinghe and Smith [J. Chem. Phys. 119, 11342 (2003)], Gee et al. [J. Chem. Theory Comput. 7, 1369 (2011)], Reiser et al. [J. Chem. Phys. 140, 044504 (2014)], and Joung and Cheatham [J. Phys. Chem. B 112, 9020 (2008)] were used along with the extended simple point charge (SPC/E) water model [Berendsen et al., J. Phys. Chem. 91, 6269 (1987)] in the simulations. In addition to the chemical potentials in solution used to obtain the activity coefficients, we also calculated the chemical potentials of salt crystals and used them to obtain the solubility of these alkali halide models in SPC/E water. The models of Weerasinghe and Smith [J. Chem. Phys. 119, 11342 (2003)] and Gee et al. [J. Chem. Theory Comput. 7, 1369 (2011)] provide excellent predictions of the mean ionic activity coefficients at 298.15 K and 1 bar, but significantly underpredict or overpredict the solubilities. The other two models generally predicted the mean ionic activity coefficients only qualitatively. With the exception of NaF for which the solubility is significantly overpredicted, the model of Joung and Cheatham predicts salt solubilities that are approximately 40%-60% of the experimental values. The models of Reiser et al. [J. Chem. Phys. 140, 044504 (2014)] make good predictions for the NaCl and NaI solubilities, but significantly underpredict the solubilities for KCl and NaF. We also tested the transferability of the models to temperatures much higher than were used to parametrize them by performing simulations for NaCl at 373.15 K and 1 bar, and at 473.15 K and 15.5 bar. All models overpredict the drop in the values of mean ionic

  2. Temperature-dependent solubilities and mean ionic activity coefficients of alkali halides in water from molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Mester, Zoltan; Panagiotopoulos, Athanassios Z.

    2015-07-01

    The mean ionic activity coefficients of aqueous KCl, NaF, NaI, and NaCl solutions of varying concentrations have been obtained from molecular dynamics simulations following a recently developed methodology based on gradual insertions of salt molecules [Z. Mester and A. Z. Panagiotopoulos, J. Chem. Phys. 142, 044507 (2015)]. The non-polarizable ion models of Weerasinghe and Smith [J. Chem. Phys. 119, 11342 (2003)], Gee et al. [J. Chem. Theory Comput. 7, 1369 (2011)], Reiser et al. [J. Chem. Phys. 140, 044504 (2014)], and Joung and Cheatham [J. Phys. Chem. B 112, 9020 (2008)] were used along with the extended simple point charge (SPC/E) water model [Berendsen et al., J. Phys. Chem. 91, 6269 (1987)] in the simulations. In addition to the chemical potentials in solution used to obtain the activity coefficients, we also calculated the chemical potentials of salt crystals and used them to obtain the solubility of these alkali halide models in SPC/E water. The models of Weerasinghe and Smith [J. Chem. Phys. 119, 11342 (2003)] and Gee et al. [J. Chem. Theory Comput. 7, 1369 (2011)] provide excellent predictions of the mean ionic activity coefficients at 298.15 K and 1 bar, but significantly underpredict or overpredict the solubilities. The other two models generally predicted the mean ionic activity coefficients only qualitatively. With the exception of NaF for which the solubility is significantly overpredicted, the model of Joung and Cheatham predicts salt solubilities that are approximately 40%-60% of the experimental values. The models of Reiser et al. [J. Chem. Phys. 140, 044504 (2014)] make good predictions for the NaCl and NaI solubilities, but significantly underpredict the solubilities for KCl and NaF. We also tested the transferability of the models to temperatures much higher than were used to parametrize them by performing simulations for NaCl at 373.15 K and 1 bar, and at 473.15 K and 15.5 bar. All models overpredict the drop in the values of mean ionic

  3. Ag-doped carbon aerogels for removing halide ions in water treatment.

    PubMed

    Sánchez-Polo, M; Rivera-Utrilla, J; Salhi, E; von Gunten, U

    2007-03-01

    The objective of this study was to analyze the efficiency of silver(Ag)-doped carbon aerogels for the removal of bromide (Br(-)) and iodide (I(-)) from drinking waters. Textural characterization of Ag-doped aerogels showed that an increase in the Ag dose added during the preparation process produced: (i) a reduction in the surface area (S(BET)) and (ii) an increase in mesopore (V(2)) and macropore (V(3)) volumes. Chemical characterization of the materials revealed an acidic surface (pH of point of zero charge, pH(PZC)=4.5, O(surface)=20%). The oxidation state of Ag was +1 and the surface concentration of this element ranged from 4% to 10%. The adsorption capacity (X(m)) and affinity of adsorbent (BX(m)) increased with a reduction in the radius of the halogenide. Furthermore, an increase in the adsorption capacity was observed with higher Ag concentrations on the aerogel surface. The high adsorption capacity of the aerogel may be due to the presence of Ag(I) on its surface, with the formation of the corresponding Ag halides. Our observations indicate that the halogenides adsorption on commercial activated carbon (Sorbo-Norit) is much lower than that of the Ag-doped carbon aerogels. The presence of chloride and natural organic matter (NOM) in the medium reduced the adsorption capacity of Br(-) and I(-) on Ag carbon aerogels. PMID:16970974

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

    NASA Astrophysics Data System (ADS)

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

    1991-03-01

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

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

    NASA Astrophysics Data System (ADS)

    Zhang, Yong

    2016-08-01

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

  6. Study on influence of growth conditions on position and shape of crystal/melt interface of alkali lead halide crystals at Bridgman growth

    NASA Astrophysics Data System (ADS)

    Král, Robert

    2012-12-01

    Suitable conditions for growth of high quality single crystals of ternary alkali lead halides prepared by a Bridgman method were explored using direct observation of a crystal/melt interface when pulling an ampoule out of a furnace, deliberated striations' induction and measurement of a temperature field in the filled ampoule in the vertical Bridgman arrangement, as model compounds lead chloride and ternary rubidium lead bromide were used. By direct observation only position of the crystal/melt interface was markedly determined, while by induced striations both the position and the shape of the interface were visualized but their contrast had to be intensified by adding admixtures. Performed temperature measurements in the filled ampoule brought both a view of temperature field in the 3D radial symmetry and basic data for comparison of a real temperature field with those obtained by projected modeling.

  7. Theoretical study of mixed LiLnX4 (Ln = La, Dy; X = F, Cl, Br, I) rare earth/alkali halide complexes.

    PubMed

    Groen, C P; Oskam, A; Kovács, A

    2000-12-25

    The structure, bonding and vibrational properties of the mixed LiLnX4 (Ln = La, Dy; X = F, Cl, Br, I) rare earth/alkali halide complexes were studied using various quantum chemical methods (HF, MP2 and the Becke3-Lee-Yang-Parr exchange-correlation density functional) in conjunction with polarized triple-zeta valence basis sets and quasi-relativistic effective core potentials for the heavy atoms. Our comparative study indicated the superiority of MP2 theory while the HF and B3-LYP methods as well as less sophisticated basis sets failed for the correct energetic relations. In particular, f polarization functions on Li and X proved to be important for the Li...X interaction in the complexes. From the three characteristic structures of such complexes, possessing 1-(C3v), 2-(C2v), or 3-fold coordination (C3v) between the alkali metal and the bridging halide atoms, the bi- and tridentate forms are located considerably lower on the potential energy surface then the monodentate isomer. Therefore only the bi- and tridentate isomers have chemical relevance. The monodentate isomer is only a high-lying local minimum in the case of X = F. For X = Cl, Br, and I this structure is found to be a second-order saddle point. The bidentate structure was found to be the global minimum for the systems with X = F, Cl, and Br. However, the relative stability with respect to the tridentate structure is very small (1-5 kJ/mol) for the heavier halide derivatives and the relative order is reversed in the case of the iodides. The energy difference between the three structures and the dissociation energy decrease in the row F to I. The ionic bonding in the complexes was characterized by natural charges and a topological analysis of the electron density distribution according to Bader's theorem. Variation of the geometrical and bonding characteristics between the lanthanum and dysprosium complexes reflects the effect of "lanthanide contraction". The calculated vibrational data indicate that

  8. Mass spectrometry of oligopeptides in the presence of large amounts of alkali halides using desorption/ionization induced by neutral cluster impact.

    PubMed

    Portz, André; Baur, Markus; Gebhardt, Christoph R; Dürr, Michael

    2016-06-01

    Oligopeptides in the presence of large amounts of salt were desorbed and ionized using desorption/ionization induced by neutral clusters (DINeC) for further analysis by means of mass spectrometry (MS). Using oligopeptides in alkali halide solutions as a model system, DINeC was shown to yield clear and fragmentation free mass spectra of the biomolecules even from environments with a large excess of salt. The results were traced back to a phase separation between salt and biomolecules during sample preparation. The ratio between alkali metal complexes [M+A](+) and bare biomolecules [M+H](+) was controlled using different preparation schemes. DINeC was applied to the products of a tryptic digest of bovine serum albumin in the presence of sodium chloride; the results of a mass fingerprint analysis did not show a major difference for the spectra with and without salt in the original solution. The metal-ion/peptide interaction was further investigated by means of tandem-MS. PMID:26825286

  9. A different view of structure-making and structure-breaking in alkali halide aqueous solutions through x-ray absorption spectroscopy.

    PubMed

    Waluyo, Iradwikanari; Nordlund, Dennis; Bergmann, Uwe; Schlesinger, Daniel; Pettersson, Lars G M; Nilsson, Anders

    2014-06-28

    X-ray absorption spectroscopy measured in transmission mode was used to study the effect of alkali and halide ions on the hydrogen-bonding (H-bonding) network of water. Cl(-) and Br(-) are shown to have insignificant effect on the structure of water while I(-) locally weakens the H-bonding, as indicated by a sharp increase of the main-edge feature in the x-ray absorption spectra. All alkali cations act as structure-breakers in water, weakening the H-bonding network. The spectral changes are similar to spectra of high density ices where the 2nd shell has collapsed due to a break-down of the tetrahedral structures, although here, around the ions, the breakdown of the local tetrahedrality is rather due to non-directional H-bonding to the larger anions. In addition, results from temperature-dependent x-ray Raman scattering measurements of NaCl solution confirm the H-bond breaking effect of Na(+) and the effect on the liquid as similar to an increase in temperature. PMID:24985653

  10. A different view of structure-making and structure-breaking in alkali halide aqueous solutions through x-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Waluyo, Iradwikanari; Nordlund, Dennis; Bergmann, Uwe; Schlesinger, Daniel; Pettersson, Lars G. M.; Nilsson, Anders

    2014-06-01

    X-ray absorption spectroscopy measured in transmission mode was used to study the effect of alkali and halide ions on the hydrogen-bonding (H-bonding) network of water. Cl- and Br- are shown to have insignificant effect on the structure of water while I- locally weakens the H-bonding, as indicated by a sharp increase of the main-edge feature in the x-ray absorption spectra. All alkali cations act as structure-breakers in water, weakening the H-bonding network. The spectral changes are similar to spectra of high density ices where the 2nd shell has collapsed due to a break-down of the tetrahedral structures, although here, around the ions, the breakdown of the local tetrahedrality is rather due to non-directional H-bonding to the larger anions. In addition, results from temperature-dependent x-ray Raman scattering measurements of NaCl solution confirm the H-bond breaking effect of Na+ and the effect on the liquid as similar to an increase in temperature.

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

    NASA Astrophysics Data System (ADS)

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

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

  12. Pressure studies of alkali, alkaline earth and rare earth doped C{sub 60} superconductors

    SciTech Connect

    Schirber, J.E.; Bayless, W.R.; Kortan, A.R.; Ozdas, E.; Zhou, O.; Murphy, D.; Fischer, J.E.

    1994-06-01

    Pressure studies of the superconducting transition temperature T{sub c} of the alkali metal doped C{sub 60} compounds helped to establish a universal curve of T{sub c} versus lattice constant upon which nearly all of these materials lie. Various theoretical schemes incorporate this finding and suggest that only the lattice parameter and not the details of the dopant determine T{sub c}. Ca{sub 5}C{sub 60}, the highest T{sub c} member of the alkaline earth doped C{sub 60} superconductor has a T{sub c} which lies on this universal curve so this material, from these considerations, should have the same large negative pressure derivative as the alkali doped superconductors. We have measured dT{sub c}/dP for Ca{sub 5}C{sub 60} and for Yb{sub x}C{sub 60} (x near 3) and find small and positive values indicating that the theoretical models must be expanded to include band structure effects.

  13. Electrical Transport Properties of C60 Single Crystals Doped with Alkali Metals

    NASA Astrophysics Data System (ADS)

    Ogata, Hironori; Maruyama, Yusei; Inabe, Tamotsu; Achiba, Yohji; Suzuki, Sinzo; Kikuchi, Koichi; Ikemoto, Isao

    Electronic structures of various kinds of alkali metal (Na, K, Rb or Cs)-doped C60 solids are studied by electrical resistivity and thermoelectric power measurements by using C60 single crystals prepared from a CS2 solution as a starting material. For K-or Rb-doped C60, metallic conducting behaviors in the normal conducting state and relatively sharp superconducting transitions are observed by the electrical resistivity measurements. Nearly linear-temperature dependences with the negative sign are observed in the thermoelectric power measurements at the normal conducting states for K-or Rb-doped C60. From electron diffusion term of the thermoelectric power, the values of Fermi energy and the density of states at the Fermi energy are estimated by assuming the three-dimensional free electron model, which are in substantial agreement with the results of other experiments and calculations. "Metal-semiconductor transition" is observed in both the electrical resistivity and the thermoelectric power measurements for Na-doped C60. Existence of metallic phase is confirmed by the thermoelectric power measurement in Cs-doped C60.

  14. First-principles Studies of the Optical Properties of Eu doped Barium Halides: From Storage Phosphor to Bright Scintillator

    NASA Astrophysics Data System (ADS)

    Canning, Andrew; Medasani, Bharat; Del Ben, Mauro; Bizarri, Gregory

    The Eu doped Ba mixed halide family BaBrX (X=F,Cl,Br,I) changes from being a widely used X-ray Storage Phosphor (BaBrF:Eu) to one of the brightest know new gamma ray detector scintillators (BaBrI:Eu). To help understand these contrasting optical properties and guide in the design of new and improved scintillator detectors, in collaboration with experimental groups, we have performed first principles theoretical studies of these materials. In particular we have studied their electron and hole trapping mechanisms and how that can explain their very different optical properties.

  15. Complete-velocity-range description of negative-ion conversion of neutral atoms on an alkali-metal-halide surface under grazing geometry

    NASA Astrophysics Data System (ADS)

    Zhou, Hu; Zhou, Wang; Zhang, Meixiao; Zhou, Lihua; Ma, Yulong; Wang, Guangyi; Wu, Yong; Li, Bowen; Chen, Ximeng

    2016-06-01

    We propose a simple theoretical approach to consider negative-ion conversion of neutral atoms grazing on alkali-metal-halide crystal surfaces over the complete velocity range. The conversion process is viewed as a series of successive binary collisions between the projectile and the negatively charged sites on the surface along their trajectories due to localization of valence-band electrons at the anionic sites of the crystal. Conversion from F0 to F- via grazing scattering in LiF(100) and KI(100) is demonstrated with this model, which incorporates the key factors of image interaction and Mott-Littleton polarization interaction for electron capture. It also incorporates the decrease in the electron affinity due to Coulomb barrier tunneling of large-velocity negative ions to the vacuum level near surface anion sites. The pronounced differences in the efficiency of F- formation at LiF(100) and KI(100) surfaces are well explained by the proposed model. The relative efficiency and related saturation of the negative-ion formation for LiF and KI crystals compare well with experimental results.

  16. Band-structure calculations of noble-gas and alkali halide solids using accurate Kohn-Sham potentials with self-interaction correction

    SciTech Connect

    Li, Y.; Krieger, J.B. ); Norman, M.R. ); Iafrate, G.J. )

    1991-11-15

    The optimized-effective-potential (OEP) method and a method developed recently by Krieger, Li, and Iafrate (KLI) are applied to the band-structure calculations of noble-gas and alkali halide solids employing the self-interaction-corrected (SIC) local-spin-density (LSD) approximation for the exchange-correlation energy functional. The resulting band gaps from both calculations are found to be in fair agreement with the experimental values. The discrepancies are typically within a few percent with results that are nearly the same as those of previously published orbital-dependent multipotential SIC calculations, whereas the LSD results underestimate the band gaps by as much as 40%. As in the LSD---and it is believed to be the case even for the exact Kohn-Sham potential---both the OEP and KLI predict valence-band widths which are narrower than those of experiment. In all cases, the KLI method yields essentially the same results as the OEP.

  17. Structural, dielectric and AC conductivity properties of Co2+ doped mixed alkali zinc borate glasses

    NASA Astrophysics Data System (ADS)

    Madhu, B. J.; Banu, Syed Asma; Harshitha, G. A.; Shilpa, T. M.; Shruthi, B.

    2013-02-01

    The Co2+ doped 19.9ZnO+5Li2CO3+25Na2CO3+50B2O3 (ZLNB) mixed alkali zinc borate glasses have been prepared by a conventional melt quenching method. The structural (XRD & FT-IR), dielectric and a.c. conductivity (σac) properties have been investigated. Amorphous nature of these glasses has been confirmed from their XRD pattern. The dielectric properties and electrical conductivity (σac) of these glasses have been studied from 100Hz to 5MHz at the room temperature. Based on the observed trends in the a.c. conductivities, the present glass samples are found to exhibit a non-Debye behavior.

  18. Optical properties of C-doped bulk GaN wafers grown by halide vapor phase epitaxy

    SciTech Connect

    Khromov, S.; Hemmingsson, C.; Monemar, B.; Hultman, L.; Pozina, G.

    2014-12-14

    Freestanding bulk C-doped GaN wafers grown by halide vapor phase epitaxy are studied by optical spectroscopy and electron microscopy. Significant changes of the near band gap (NBG) emission as well as an enhancement of yellow luminescence have been found with increasing C doping from 5 × 10{sup 16} cm{sup −3} to 6 × 10{sup 17} cm{sup −3}. Cathodoluminescence mapping reveals hexagonal domain structures (pits) with high oxygen concentrations formed during the growth. NBG emission within the pits even at high C concentration is dominated by a rather broad line at ∼3.47 eV typical for n-type GaN. In the area without pits, quenching of the donor bound exciton (DBE) spectrum at moderate C doping levels of 1–2 × 10{sup 17} cm{sup −3} is observed along with the appearance of two acceptor bound exciton lines typical for Mg-doped GaN. The DBE ionization due to local electric fields in compensated GaN may explain the transformation of the NBG emission.

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

    NASA Astrophysics Data System (ADS)

    Hebard, Arthur

    2008-03-01

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

  20. Characterization of an Alkali- and Halide-Resistant Laccase Expressed in E. coli: CotA from Bacillus clausii

    PubMed Central

    Brander, Søren; Mikkelsen, Jørn D.; Kepp, Kasper P.

    2014-01-01

    The limitations of fungal laccases at higher pH and salt concentrations have intensified the search for new extremophilic bacterial laccases. We report the cloning, expression, and characterization of the bacterial cotA from Bacillus clausii, a supposed alkalophilic ortholog of cotA from B. subtilis. Both laccases were expressed in E. coli strain BL21(DE3) and characterized fully in parallel for strict benchmarking. We report activity on ABTS, SGZ, DMP, caffeic acid, promazine, phenyl hydrazine, tannic acid, and bilirubin at variable pH. Whereas ABTS, promazine, and phenyl hydrazine activities vs. pH were similar, the activity of B. clausii cotA was shifted upwards by ∼0.5–2 pH units for the simple phenolic substrates DMP, SGZ, and caffeic acid. This shift is not due to substrate affinity (KM) but to pH dependence of catalytic turnover: The kcat of B. clausii cotA was 1 s−1 at pH 6 and 5 s−1 at pH 8 in contrast to 6 s−1 at pH 6 and 2 s−1 at pH 8 for of B. subtilis cotA. Overall, kcat/KM was 10-fold higher for B. subtilis cotA at pHopt. While both proteins were heat activated, activation increased with pH and was larger in cotA from B. clausii. NaCl inhibited activity at acidic pH, but not up to 500–700 mM NaCl in alkaline pH, a further advantage of the alkali regime in laccase applications. The B. clausii cotA had ∼20 minutes half-life at 80°C, less than the ∼50 minutes at 80°C for cotA from B. subtilis. While cotA from B. subtilis had optimal stability at pH∼8, the cotA from B. clausii displayed higher combined salt- and alkali-resistance. This resistance is possibly caused by two substitutions (S427Q and V110E) that could repel anions to reduce anion-copper interactions at the expense of catalytic proficiency, a trade-off of potential relevance to laccase optimization. PMID:24915287

  1. Characterization of an alkali- and halide-resistant laccase expressed in E. coli: CotA from Bacillus clausii.

    PubMed

    Brander, Søren; Mikkelsen, Jørn D; Kepp, Kasper P

    2014-01-01

    The limitations of fungal laccases at higher pH and salt concentrations have intensified the search for new extremophilic bacterial laccases. We report the cloning, expression, and characterization of the bacterial cotA from Bacillus clausii, a supposed alkalophilic ortholog of cotA from B. subtilis. Both laccases were expressed in E. coli strain BL21(DE3) and characterized fully in parallel for strict benchmarking. We report activity on ABTS, SGZ, DMP, caffeic acid, promazine, phenyl hydrazine, tannic acid, and bilirubin at variable pH. Whereas ABTS, promazine, and phenyl hydrazine activities vs. pH were similar, the activity of B. clausii cotA was shifted upwards by ~0.5-2 pH units for the simple phenolic substrates DMP, SGZ, and caffeic acid. This shift is not due to substrate affinity (K(M)) but to pH dependence of catalytic turnover: The k(cat) of B. clausii cotA was 1 s⁻¹ at pH 6 and 5 s⁻¹ at pH 8 in contrast to 6 s⁻¹ at pH 6 and 2 s⁻¹ at pH 8 for of B. subtilis cotA. Overall, k(cat)/K(M) was 10-fold higher for B. subtilis cotA at pH(opt). While both proteins were heat activated, activation increased with pH and was larger in cotA from B. clausii. NaCl inhibited activity at acidic pH, but not up to 500-700 mM NaCl in alkaline pH, a further advantage of the alkali regime in laccase applications. The B. clausii cotA had ~20 minutes half-life at 80°C, less than the ~50 minutes at 80°C for cotA from B. subtilis. While cotA from B. subtilis had optimal stability at pH~8, the cotA from B. clausii displayed higher combined salt- and alkali-resistance. This resistance is possibly caused by two substitutions (S427Q and V110E) that could repel anions to reduce anion-copper interactions at the expense of catalytic proficiency, a trade-off of potential relevance to laccase optimization. PMID:24915287

  2. Pre- and initial stages of epitaxy in alkali halide systems. II. Interaction of molecular beams of CsCl with (100) surfaces of NaCl

    NASA Astrophysics Data System (ADS)

    Dabringhaus, H.; Haag, M.

    The interaction of molecular beams of CsCl with (100) surfaces of NaCl is studied for crystal temperatures between 560 and 620 K and for molecular beam fluxes between 2 × 10 7 and 2 × 10 13 cm -2 s -1 by measurements of transient and steady state desorption fluxes, by static SIMS, and by electron microscopy. Also for the large Cs + ions a fast cation exchange Cs + ⇌ Na + between CsCl molecules adsorbed on the terrace and the outermost surface layer of the NaCl crystal is observed. The results for undersaturation are interpreted by incorporation of Cs + ions in the outermost surface layer of the NaCl crystal and by adsorption of CsCl molecules at the monatomic steps on the surface. The outermost surface layer proves to have a maximum capacity for Cs + of 2.4 × 10 11 cm -2. The residence time of Cs + ions in the outermost surface layer is determined as τ0 = 1.6 × 10 -12 exp(1.49 (eV)/ kT), the time for desorption of CsCl molecules from the monatomic steps as τ1 = 2.9 × 10 -14 exp(1.60 (eV)/ kT). By experiments with an additional NaCl flux onto the surface it is shown that τ0 is the time for a back-exchange of Cs + ions from the outermost surface layer against Na + from NaCl admolecules. For supersaturation the growth of polymorphic CsCl islands is observed. In the first growth stages these islands show the NaCl-type structure, while for later growth stages the CsCl type structure is found. A comparative discussion of all studied alkali halide systems shows that the different results can be attributed to the different radii of guest and host cation and to lattice misfits, respectively.

  3. Alkali halide-assisted penetration of neostigmine across excised human skin: a combination of structured water disruption and a Donnan-like effect.

    PubMed

    Michael-Baruch, E; Shiri, Y; Cohen, S

    1994-08-01

    The penetration of neostigmine across excised human skin mounted in flow-through diffusion cells, delivered from a 0.28 M aqueous solution, was below detection limits. The presence of either NaCl or LiCl in the donor solution caused significant fluxes of neostigmine, with permeability coefficients (Kp's) in the range of 10(-6) cm min-1. Paradoxically, low concentrations of NaCl or LiCl (0.25 and 0.5 M) were more effective in this respect than the 1 M solution, which was the least effective concentration in the range of 0.25-3 M. Thus, the dependence of the experimental Kp values on inorganic ion concentration followed a biphasic course, suggesting the participation of two distinctive mechanisms in the penetration-enhancement process. The early phase corresponding to 0.25 and 0.5 M NaCl or LiCl is being partly ascribed to a decrease in the viscosity of lamellar water caused by the influx of the respective hydrated ions, hydration of LiCl or NaCl being more extensive at low alkali halide concentration that at higher ones (reference cited). The late phase corresponding to 2 and 3 M LiCl and NaCl is partly ascribed to a Donnan-like effect whereby the presence of a large excess of poorly diffusible common ion (Na+ or Li+) enhances the partitioning into the skin of the more diffusible ion, in this case neostigmine cation. The presence of inorganic ions at different concentrations had no effect on the partial molal volume of neostigmine bromide (Vi infinity = 223.5 cm3 mol-1), which was practically the same for all concentrations of either LiCl and NaCl.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:7983588

  4. XPS studies and photocurrent applications of alkali-metals-doped ZnO nanoparticles under visible illumination conditions

    NASA Astrophysics Data System (ADS)

    Saáedi, Abdolhossein; Yousefi, Ramin; Jamali-Sheini, Farid; Zak, Ali Khorsand; Cheraghizade, Mohsen; Mahmoudian, M. R.; Baghchesara, Mohammad Amin; Dezaki, Abbas Shirmardi

    2016-05-01

    The present work is a study about a relationship between X-ray photoelectron spectrometer (XPS) results and photocurrent intensity of alkali-metals-elements doped ZnO nanoparticles, which is carried out under visible illumination conditions. The nanoparticles were synthesized by a simple sol-gel method. Structure and morphology studies of the NPs were carried out by X-ray diffraction analysis (XRD) and transmission electron microscopy (TEM). The effect of doping on the optical band-gap was investigated by using UV-visible spectrometer. The absorption peak of the doped ZnO NPs was red-shifted with respect to that of the undoped ZnO NPs. After that, the photocurrent application of the products was examined under a white light source at 2 V bias. The photocurrent results showed that, the current intensity of the ZnO NPs was increased by doping materials. However, K-doped ZnO NPs showed the highest photocurrent intensity. Finally, a discussion was carried out about the obtained photocurrent results by the O-1s spectra of the XPS of the samples. Our results suggest that the alkali-metals-doped ZnO NPs exhibit considerable promise for highly sensitive visible-light photodetectors.

  5. From T2,2@Bmmim to Alkali@T2,2@Bmmim Ivory Ball-like Clusters: Ionothermal Syntheses, Precise Doping, and Photocatalytic Properties.

    PubMed

    Du, Cheng-Feng; Li, Jian-Rong; Zhang, Bo; Shen, Nan-Nan; Huang, Xiao-Ying

    2015-06-15

    Presented here are the syntheses, structures, and properties of an In-Sn-Se compound based on a ternary super-supertetrahedral T2,2 cluster nested by Bmmim cations and two of its alkali-doped quaternary analogues. By means of a one-pot ionothermal method, an alkali metal ion (Cs(+) or Rb(+)) could be precisely doped into the central cavity of the cluster, forming an alkali@T2,2@Bmmim quaternary cluster. Remarkably, the undoped compound exhibited excellent stability and visible light photodegradation ability over a wide range of pH, especially in acidic conditions. PMID:26034842

  6. Unified understanding of superconductivity and Mott transition in alkali-doped fullerides from first principles.

    PubMed

    Nomura, Yusuke; Sakai, Shiro; Capone, Massimo; Arita, Ryotaro

    2015-08-01

    Alkali-doped fullerides A 3C60 (A = K, Rb, Cs) are surprising materials where conventional phonon-mediated superconductivity and unconventional Mott physics meet, leading to a remarkable phase diagram as a function of volume per C60 molecule. We address these materials with a state-of-the-art calculation, where we construct a realistic low-energy model from first principles without using a priori information other than the crystal structure and solve it with an accurate many-body theory. Remarkably, our scheme comprehensively reproduces the experimental phase diagram including the low-spin Mott-insulating phase next to the superconducting phase. More remarkably, the critical temperatures T c's calculated from first principles quantitatively reproduce the experimental values. The driving force behind the surprising phase diagram of A 3C60 is a subtle competition between Hund's coupling and Jahn-Teller phonons, which leads to an effectively inverted Hund's coupling. Our results establish that the fullerides are the first members of a novel class of molecular superconductors in which the multiorbital electronic correlations and phonons cooperate to reach high T c s-wave superconductivity. PMID:26601242

  7. Physical, structural and spectroscopic investigations of Sm3+ doped ZnO mixed alkali borate glass

    NASA Astrophysics Data System (ADS)

    Sailaja, B.; Joyce Stella, R.; Thirumala Rao, G.; Jaya Raja, B.; Pushpa Manjari, V.; Ravikumar, R. V. S. S. N.

    2015-09-01

    Glass of 20ZnO-15 Li2O-15 Na2O-49.9 B2O3 doped with 0.1 mol% of Sm3+ (ZLNB) was prepared by the melt quenching technique. Physical properties were studied and analysed. The XRD studies confirm the amorphous nature of sample. The FT-IR spectral investigation discloses the BO3, BO4 groups, H and OH bonds. Optical absorption and emission spectra were recorded and characterized. Judd-Ofelt theory was applied to f ↔ f transitions to evaluate Judd-Ofelt intensity parameters (Ωλ). The oscillator strengths and bonding parameters were determined from absorption spectra. The trend observed was Ω4 > Ω6 > Ω2. High value of Ω4 reveals higher rigidity and covalency around the Sm3+ ion. Low value of Ω2 implies ionic nature of ligands and site symmetry around Sm3+ ion. luminescence data and Judd-Ofelt parameters Ωλ (λ = 2, 4, and 6) were used to evaluate various radiative probabilities like spontaneous radiative emission probabilities (AR), radiative lifetime (τR) and branching ratios (βR) stimulated emission cross section (σe) and CIE colour coordinates were measured, CCT temperature evaluated and the values were used to ascertain potential laser transitions at the optimum mixed alkali effect observed for the glass sample prepared. The preparedness of the material as the efficient laser active material is examined.

  8. Structure and Dynamics of Tunneling and Laser - Defects in Alkali Halides as Studied by a Behavior Type Analysis of the Polarized Raman Scattering.

    NASA Astrophysics Data System (ADS)

    Joosen, Wim M. C.

    It is demonstrated that proper analysis of polarized Raman spectra of defects in alkali halides by means of the Behavior Type (BT) method allows a detailed description of defect dynamics. The recently developed BT method provides a systematic procedure to distinguish, among the 125 Raman -active modes of the 33 possible point groups of a defect in a cubic lattice, the Raman modes which are consistent with the polarized Raman data, from those which are not. The efficiency of the BT method was shown in the interpretation of the low frequency Raman mode at 43 cm ^{-1} of the Li ^+ off-center impurity in KCl, which was attributed to a collective motion of the surrounding chlorine ions. This experimental finding inspired us to calculate the time dependent phonon autocorrelation function of a coupled spin-phonon system, which explains the anomalous isotope shift of the low frequency mode. We also studied the hydrogen-tagged Li ^+ center in KCl, which performs a correlated tunneling motion and put forward a defect model, in which the Li^+ ion and the hydrogen atom are both accommodated on the same cation site and displaced along <111> in opposite directions. There is no preferential molecular bond of any consequence between them. Our picture modifies the model based on electron spin resonance measurements, in which the H^{0}Li ^+ center is considered as a (LiH) ^+ molecular system. The Tl^0(1) defect is the first laser-center of the atomic type investigated with the Raman technique. The polarized Raman spectra, were excited in the third optical band of Tl^0 (1) and show that this transition is broadened by A_1-modes of the C_ {rm 4v} defect symmetry. We distinguished an induced first order spectrum, shown to be characteristic for the KCl lattice, and a low frequency vibration at about 30 cm^{-1}, which reflects the motion of the thallium atom along the fourfold axis. The Tl^+Tl^0 (1) center provided a first test-case for the extended BT method for resonant Raman

  9. Electrolytic systems and methods for making metal halides and refining metals

    SciTech Connect

    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.

  10. Homogeneity of bismuth-distribution in bismuth-doped alkali germanate laser glasses towards superbroad fiber amplifiers.

    PubMed

    Zhao, Yanqi; Wondraczek, Lothar; Mermet, Alain; Peng, Mingying; Zhang, Qinyuan; Qiu, Jianrong

    2015-05-01

    Compared to rare-earth doped glasses, bismuth-doped glasses hold promise for super-broadband near-infrared (NIR) photoemission and potential applications in optical amplification. However, optically active bismuth centers are extremely sensitive to the properties of the surrounding matrix, and also to processing conditions. This is strongly complicating the exploitation of this class of materials, because functional devices require a very delicate adjustment of the redox state of the bismuth species, and its distribution throughout the bulk of the material. It also largely limits some of the conventional processing routes for glass fiber, which start from gas phase deposition and may require very high processing temperature. Here, we investigate the influence of melting time and alkali addition on bismuth-related NIR photoluminescence from melt-derived germanate glasses. We show that the effect of melting time on bismuth-related absorption and NIR photoemission is primarily through bismuth volatilization. Adding alkali oxides as fluxing agents, the melt viscosity can be lowered to reduce either the glass melting temperature, or the melting time, or both. At the same time, however, alkali addition also leads to increasing mean-field basicity, what may reduce the intensity of bismuth-related NIR emission. Preferentially using Li2O over Na2O or K2O presents the best trade-off between those above factors, because its local effect may be adverse to the generally assumed trend of the negative influence of more basic matrix composition. This observation provides an important guideline for the design of melt-derived Bi-doped glasses with efficient NIR photoemission and high optical homogeneity. PMID:25969328

  11. Distinct Impact of Alkali-Ion Doping on Electrical Transport Properties of Thermoelectric p-Type Polycrystalline SnSe.

    PubMed

    Wei, Tian-Ran; Tan, Gangjian; Zhang, Xiaomi; Wu, Chao-Feng; Li, Jing-Feng; Dravid, Vinayak P; Snyder, G Jeffrey; Kanatzidis, Mercouri G

    2016-07-20

    Recent findings about ultrahigh thermoelectric performance in SnSe single crystals have stimulated related research on this simple binary compound, which is focused mostly on its polycrystalline counterparts, and particularly on electrical property enhancement by effective doping. This work systematically investigated the thermoelectric properties of polycrystalline SnSe doped with three alkali metals (Li, Na, and K). It is found that Na has the best doping efficiency, leading to an increase in hole concentration from 3.2 × 10(17) to 4.4 × 10(19) cm(-3) at room temperature, accompanied by a drop in Seebeck coefficient from 480 to 142 μV/K. An equivalent single parabolic band model was found adequate to capture the variation tendency of Seebeck coefficient with doping levels within a wide range. A mixed scattering of carriers by acoustic phonons and grain boundaries is suitable for numerically understanding the temperature-dependence of carrier mobility. A maximum ZT of ∼0.8 was achieved in 1% Na- or K-doped SnSe at 800 K. Possible strategies to improve the mobility and ZT of polycrystals were also proposed. PMID:27348333

  12. Structural and electronic engineering of 3DOM WO3 by alkali metal doping for improved NO2 sensing performance.

    PubMed

    Wang, Zhihua; Fan, Xiaoxiao; Han, Dongmei; Gu, Fubo

    2016-05-19

    Novel alkali metal doped 3DOM WO3 materials were prepared using a simple colloidal crystal template method. Raman, XRD, SEM, TEM, XPS, PL, Hall and UV-Vis techniques were used to characterize the structural and electronic properties of all the products, while the corresponding sensing performances targeting ppb level NO2 were determined at different working temperatures. For the overall goal of structural and electronic engineering, the co-effect of structural and electronic properties on the improved NO2 sensing performance of alkali metal doped 3DOM WO3 was studied. The test results showed that the gas sensing properties of 3DOM WO3/Li improved the most, with the fast response-recovery time and excellent selectivity. More importantly, the response of 3DOM WO3/Li to 500 ppb NO2 was up to 55 at room temperature (25 °C). The especially high response to ppb level NO2 at room temperature (25 °C) in this work has a very important practical significance. The best sensing performance of 3DOM WO3/Li could be ascribed to the most structure defects and the highest carrier mobility. And the possible gas sensing mechanism based on the model of the depletion layer was proposed to demonstrate that both structural and electronic properties are responsible for the NO2 sensing behavior. PMID:27109698

  13. Effect of Li 2O content on physical and structural properties of vanadyl doped alkali zinc borate glasses

    NASA Astrophysics Data System (ADS)

    Raghavendra Rao, T.; Rama Krishna, Ch.; Udayachandran Thampy, U. S.; Venkata Reddy, Ch.; Reddy, Y. P.; Sambasiva Rao, P.; Ravikumar, R. V. S. S. N.

    2011-05-01

    The effect of Li 2O content in vanadyl doped 20ZnO+ xLi 2O+(30- x)Na 2O+50B 2O 3 (5≤ x≥25) glasses has been studied with respect to their physical and structural properties. The absence of sharp peaks in XRD spectra of these glass samples confirms the amorphous nature. The physical parameters like density, refractive index, ionic concentration and electronic polarizability vary non-linearly with x mol% depending on the diffusivities of alkali ions. EPR and optical absorption spectra reveal that the resonance signals are characteristics of VO 2+ ions in tetragonally compressed octahedral site. Spin-Hamiltonian, crystal field, tetragonal field and bonding parameters are found to be in good agreement with the other reported glass systems. The tetragonal distortion ( g⊥- g∥) and Dt reveals that their values vary non-linearly with Li 2O content and reaches a minimum at x=10 mol%. An anomaly of character has been observed in all the properties of vanadyl doped glass systems, which gives a clear indication of mixed alkali effect.

  14. Theoretical Studies of the Optical Properties of Eu doped Barium Mixed Halides: From X-ray Storage Phosphor to Bright Scintillator

    NASA Astrophysics Data System (ADS)

    Chourou, Slim; Bizarri, Gregory; Canning, Andrew

    2015-03-01

    The Eu doped Ba mixed halide family BaBrX (X=F,Cl,Br,I) changes from being a widely used X-ray Storage Phosphor (BaBrF:Eu) to one of the brightest know new gamma ray detector scintillators (BaBrI:Eu). To help understand these contrasting optical properties and guide in the design of new and improved scintillator detectors, in collaboration with experimental groups, we have performed first principles theoretical studies of these materials. In particular we have studied their electron and hole trapping mechanisms and how that can explain their very different optical properties.

  15. Direct imaging of the alkali metal site in K-doped fullerene peapods.

    PubMed

    Guan, Lunhui; Suenaga, Kazu; Shi, Zujin; Gu, Zhennan; Iijima, Sumio

    2005-02-01

    The structure of K-doped fullerene peapods has been investigated by means of high-resolution transmission electron microscopy and electron energy-loss spectroscopy (EELS). It is proven that the potassium atoms can be doped at the intermolecular sites within C60 peapods. The EELS spectrum of potassium (K) L edge clearly exhibits the feature of K+ in the doped peapod and consequently suggests n-type doping. These results encourage the realization of a one-dimensional superconducting wire based on the nanotube peapods. PMID:15783568

  16. Structural and electronic engineering of 3DOM WO3 by alkali metal doping for improved NO2 sensing performance

    NASA Astrophysics Data System (ADS)

    Wang, Zhihua; Fan, Xiaoxiao; Han, Dongmei; Gu, Fubo

    2016-05-01

    Novel alkali metal doped 3DOM WO3 materials were prepared using a simple colloidal crystal template method. Raman, XRD, SEM, TEM, XPS, PL, Hall and UV-Vis techniques were used to characterize the structural and electronic properties of all the products, while the corresponding sensing performances targeting ppb level NO2 were determined at different working temperatures. For the overall goal of structural and electronic engineering, the co-effect of structural and electronic properties on the improved NO2 sensing performance of alkali metal doped 3DOM WO3 was studied. The test results showed that the gas sensing properties of 3DOM WO3/Li improved the most, with the fast response-recovery time and excellent selectivity. More importantly, the response of 3DOM WO3/Li to 500 ppb NO2 was up to 55 at room temperature (25 °C). The especially high response to ppb level NO2 at room temperature (25 °C) in this work has a very important practical significance. The best sensing performance of 3DOM WO3/Li could be ascribed to the most structure defects and the highest carrier mobility. And the possible gas sensing mechanism based on the model of the depletion layer was proposed to demonstrate that both structural and electronic properties are responsible for the NO2 sensing behavior.Novel alkali metal doped 3DOM WO3 materials were prepared using a simple colloidal crystal template method. Raman, XRD, SEM, TEM, XPS, PL, Hall and UV-Vis techniques were used to characterize the structural and electronic properties of all the products, while the corresponding sensing performances targeting ppb level NO2 were determined at different working temperatures. For the overall goal of structural and electronic engineering, the co-effect of structural and electronic properties on the improved NO2 sensing performance of alkali metal doped 3DOM WO3 was studied. The test results showed that the gas sensing properties of 3DOM WO3/Li improved the most, with the fast response-recovery time and

  17. MEA for alkaline direct ethanol fuel cell with alkali doped PBI membrane and non-platinum electrodes

    NASA Astrophysics Data System (ADS)

    Modestov, A. D.; Tarasevich, M. R.; Leykin, A. Yu.; Filimonov, V. Ya.

    This paper reports on the fabrication of MEA for alkaline direct ethanol fuel cell (ADEFC). The MEA was fabricated using non-platinum electrocatalysts and a membrane of alkali doped polybenzimidazole (PBI). The employed oxygen reduction catalyst was prepared by pyrolysis of 5,10,15,20-tetrakis(4-methoxyphenyl)-21H,23H-porphine cobalt(II) supported on XC72 carbon. This catalyst is tolerant to ethanol. Electrocatalyst at the anode was RuV alloy supported on XC72 carbon. It was synthesized by reduction of respective salts at elevated temperature. Single cell power density of 100 mW cm -2 at U = 0.4 V was achieved at 80 °C using air at ambient pressure and 3 M KOH + 2 M EtOH anode feed. The developed MEA is considered viable for use in emergency power supply units and in power sources for portable electronic equipment.

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

    NASA Astrophysics Data System (ADS)

    Sasi Kumar, M. V.; Rajesh, D.; Balakrishna, A.; Ratnakaram, Y. C.

    2013-04-01

    In the present investigation a new series of six different Nd3+ doped alkali and mixed alkali (Li, Na, K, Li-Na, Li-K and Na-K) heavy metal (PbO and ZnO) borate glasses were prepared using the melt quenching technique. The amorphous nature of the glass systems has been identified based on the X-ray diffraction analysis. The glass transition studies were carried out using differential scanning calorimetry (DSC). Optical properties were studied by measuring the optical absorption and near infrared luminescence spectra. The Judd-Ofelt (J-O) theory has been applied to calculate J-O intensity parameters, Ωλ (λ=2, 4 and 6) and in turn used to estimate radiative properties of certain transitions. Spectroscopic parameters such as transition probabilities (AT), branching ratios (β), radiative lifetimes (τR) and integrated absorption cross-sections (Σ) were calculated using J-O intensity parameters for all transitions. Using emission spectra, experimental branching ratios and stimulated emission cross-sections (σP) are obtained for all the observed emission transitions.

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

    NASA Astrophysics Data System (ADS)

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

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

  20. Heat capacity of molten halides.

    PubMed

    Redkin, Alexander A; Zaikov, Yurii P; Korzun, Iraida V; Reznitskikh, Olga G; Yaroslavtseva, Tatiana V; Kumkov, Sergey I

    2015-01-15

    The heat capacities of molten salts are very important for their practical use. Experimental investigation of this property is challenging because of the high temperatures involved and the corrosive nature of these materials. It is preferable to combine experimental investigations with empirical relationships, which allows for the evaluation of the heat capacity of molten salt mixtures. The isobaric molar heat capacities of all molten alkali and alkaline-earth halides were found to be constant for each group of salts. The value depends on the number of atoms in the salt, and the molar heat capacity per atom is constant for all molten halide salts with the exception of the lithium halides. The molar heat capacities of molten halides do not change when the anions are changed. PMID:25530462

  1. Characterization of Cr3+ doped mixed alkali ions effect in zinc borate glasses - Physical and spectroscopic investigations

    NASA Astrophysics Data System (ADS)

    Rama Sundari, G.; Pushpa Manjari, V.; Raghavendra Rao, T.; Satish, D. V.; Rama Krishna, Ch.; Venkata Reddy, Ch.; Ravikumar, R. V. S. S. N.

    2014-06-01

    The physical and structural properties of Cr3+ doped 19.9 ZnO + xLi2O + (30 - x) Na2O + 50B2O3 (5 ⩽ x ⩽ 25) (ZLNB) glasses have been studied. Powder X-ray diffraction patterns indicated the amorphous nature of the glass samples. The physical parameters of all the glasses were also evaluated with respect to the composition. They exhibit the non-linearity providing the evidence for mixed alkali ions effect. The infrared spectra of the glasses in the range 400-4000 cm-1 showed the presence of BO3 and BO4 local structures in all the glass systems. No boroxol ring formation was observed in the structure of these glasses. Optical absorption and electron paramagnetic resonance studies were carried out at room temperature. From the optical absorption data various optical parameters such as optical band gap, Urbach energy were evaluated. Crystal field and Racah parameters are evaluated from optical absorption spectra. The EPR spectra of Cr3+ doped ZLNB glasses exhibited resonance signals at g = 4.066 and g = 1.9779 characteristic of Cr3+ ions. The evaluated bonding parameters suggest the covalent nature.

  2. Alkali doped poly (2,5-benzimidazole) membrane for alkaline water electrolysis: Characterization and performance

    NASA Astrophysics Data System (ADS)

    Diaz, Liliana A.; Hnát, Jaromír; Heredia, Nayra; Bruno, Mariano M.; Viva, Federico A.; Paidar, Martin; Corti, Horacio R.; Bouzek, Karel; Abuin, Graciela C.

    2016-04-01

    The properties and performance of linear and cross-linked KOH doped ABPBI membranes as electrolyte/separator for zero gap alkaline water electrolysis cells are evaluated and compared with a commercial Zirfon® diaphragm. Stability in alkaline environment, swelling, thermal properties, water sorption, KOH uptake and conductivity of linear (L-ABPBI) and cross-linked (C-ABPBI) membranes doped with different concentrations of KOH are analyzed. Linear membranes show stability up to 3.0 mol·dm-3 KOH doping, while cross-linked membranes are stable up to 4.2 mol·dm-3 KOH doping. Both kinds of membranes exhibit good thermal stability and reasonable specific ionic conductivity at 22 °C in the range between 7 and 25 mS·cm-1, being slightly higher the conductivity of C-ABPBI membranes than that of L-ABPBI ones. In short-term electrolysis tests both L-ABPBI and C-ABPBI membranes show better performance than Zirfon diaphragm in the range from 50 to 70 °C. A current density of 335 mA·cm-2 at a cell voltage of 2.0 V is attained with C-ABPBI membranes doped in 3 mol·dm-3 KOH at 70 °C, a performance comparable with that of commercial units operating at temperatures ca. 80 °C and 30 wt% KOH (6.7 mol·dm-3) as electrolyte.

  3. Crystal growth and near infrared optical properties of Pr 3+ doped lead halide materials for resonantly pumped eye safe laser applications

    NASA Astrophysics Data System (ADS)

    Jones, Ivy Krystal

    In this dissertation the material development and optical spectroscopy of Pr3+ activated low phonon energy halide crystals is presented for possible applications in resonantly pumped eye-safe solid-state laser gain media. In the last twenty years, the developments in fiber and diode lasers have enabled highly efficient resonant pumping of Pr3+ doped crystals for possible lasing in the 1.6--1.7 microm region. In this work, the results of the purification, crystal growth, and near-infrared (NIR) spectroscopic characterization of Pr3+ doped lead (II) chloride, PbCl2 and lead (II) bromide, PbBr2 are presented. The investigated PbCl2 and PbBr2 crystals are non-hygroscopic with maximum phonon energies between ~180--200 cm-1, which enable efficient emission in the NIR spectral region (~ 1.6 microm) from the 3F3/3F4 → 3H4 transition of Pr3+ ions. The commercial available starting materials were purchased as ultra dry, high purity (~ 99.999 %) beads and purified through a combination of zone-refinement and halogenation. The crystal growth of Pr3+ doped PbCl 2 and PbBr2 was performed via vertical Bridgman technique using a two-zone furnace. The resulting Pr3+ doped PbCl 2 and PbBr2 crystals exhibited characteristic IR absorption bands in the 1.5--1.7 microm region (3H4 → 3F3/3F4), which allow for resonant pumping using commercial diode lasers. A broad IR emission band centered at ~1.6 microm was observed under ~1445 nm diode laser excitation from both Pr3+ doped halides. This dissertation presents comparative spectroscopic results for Pr 3+:PbCl2 and Pr3+:PbBr2 including NIR absorption and emission studies, lifetime measurements, modelling of radiative and non-radiative decay rates, determination of transition cross-section, and the net effective gain cross sections.

  4. Color of pure and alkali-doped cerium sulfide: A local-density-functional study

    NASA Astrophysics Data System (ADS)

    Perrin, M.-A.; Wimmer, E.

    1996-07-01

    The electronic structure and mechanisms for the optical excitations of pure and Na-doped γ-Ce2S3 have been investigated using first-principles local-density-functional theory. The energy-band structures from augmented-spherical-wave calculations indicate that the S 3p-->Ce 5d interband transitions give rise to absorptions in the ultraviolet, whereas the observed red color of γ-Ce2S3 is associated with localized Ce 4f-->5d excitations. The cationic vacancies in γ-Ce2S3 (which is derived from the cubic Th3P4 structure) lead to the formation of vacancy bands, which are split off from the top of the S 3p valence band. Na doping removes these vacancy bands and homogenizes the band edges of the valence and conduction bands. As a consequence, the onset of the f-->d transitions is shifted slightly to larger energies and becomes sharper, which is consistent with an observed change in the color of γ-Ce2S3 from maroon to red-orange upon doping with Na.

  5. Oxidation of hydrogen halides to elemental halogens

    DOEpatents

    Rohrmann, Charles A.; Fullam, Harold T.

    1985-01-01

    A process for oxidizing hydrogen halides having substantially no sulfur impurities by means of a catalytically active molten salt is disclosed. A mixture of the subject hydrogen halide and an oxygen bearing gas is contacted with a molten salt containing an oxidizing catalyst and alkali metal normal sulfates and pyrosulfates to produce an effluent gas stream rich in the elemental halogen and substantially free of sulfur oxide gases.

  6. Structural investigation and electron paramagnetic resonance of vanadyl doped alkali niobium borate glasses.

    PubMed

    Agarwal, A; Sheoran, A; Sanghi, S; Bhatnagar, V; Gupta, S K; Arora, M

    2010-03-01

    Glasses with compositions xNb(2)O(5).(30-x)M(2)O.69B(2)O(3) (where M=Li, Na, K; x=0, 4, 8 mol%) doped with 1 mol% V(2)O(5) have been prepared using normal melt quench technique. The IR transmission spectra of the glasses have been studied over the range 400-4000 cm(-1). The changes caused by the addition of Nb(2)O(5) on the structure of these glasses have been reported. The electron paramagnetic resonance spectra of VO(2+) ions in these glasses have been recorded in X-band (9.14 GHz) at room temperature (300 K). The spin Hamiltonian parameters, dipolar hyperfine coupling parameter and Fermi contact interaction parameter have been calculated. It is observed that the resultant resonance spectra contain hyperfine structures (hfs) due to V(4+) ions which exist as VO(2+) ions in octahedral coordination with a tetragonal compression in the present glasses. The tetragonality of V(4+)O(6) complex decreases with increasing concentration of Nb(2)O(5). The 3d(xy) orbit contracts with increase in Nb(2)O(5):M(2)O ratio. Values of the theoretical optical basicity, Lambda(th), have also been reported. PMID:20060775

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

    NASA Technical Reports Server (NTRS)

    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).

  8. Molecular compressibility of some halides in alcohols

    NASA Technical Reports Server (NTRS)

    Serban, C.; Auslaender, D.

    1974-01-01

    After measuring ultrasonic velocity and density, the molecular compressibility values from Wada's formula were calculated, for alkali metal halide solutions in methyl, ethyl, butyl, and glycol alcohol. The temperature and concentration dependence were studied, finding deviations due to the hydrogen bonds of the solvent.

  9. Robust s± superconductivity in a two-band Hubbard-Fröhlich model of alkali-doped organics

    NASA Astrophysics Data System (ADS)

    Qin, Tao; Fabrizio, Michele; Naghavi, S. Shahab; Tosatti, Erio

    2014-08-01

    The damaging effect of strong electron-electron repulsion on regular, electron-phonon superconductivity is a standard tenet. In spite of that, an increasing number of compounds such as fullerides and more recently alkali-doped aromatics exhibit superconductivity despite very narrow bands and very strong electron repulsion. Here, we explore superconducting solutions of a model Hamiltonian inspired by the electronic structure of alkali-doped aromatics. The model is a two-site, two-narrow-band metal with a single intersite phonon, leading to attraction-mediated, two-order parameter superconductivity. On top of that, the model includes a repulsive onsite Hubbard U, whose effect on the superconductivity we study. Starting within mean field, we find that s± superconductivity is the best solution surviving the presence of U, whose effect is canceled out by the opposite signs of the two order parameters. The correlated Gutzwiller study that follows is necessary because without electron correlations, the superconducting state would in this model be superseded by an antiferromagnetic insulating state with lower energy. The Gutzwiller correlations lower the energy of the metallic state, with the consequence that the s± superconducting state is stabilized and even strengthened for small Hubbard U.

  10. Computation of methodology-independent single-ion solvation properties from molecular simulations. IV. Optimized Lennard-Jones interaction parameter sets for the alkali and halide ions in water

    SciTech Connect

    Reif, Maria M.; Huenenberger, Philippe H.

    2011-04-14

    The raw single-ion solvation free energies computed from atomistic (explicit-solvent) simulations are extremely sensitive to the boundary conditions and treatment of electrostatic interactions used during these simulations. However, as shown recently [M. A. Kastenholz and P. H. Huenenberger, J. Chem. Phys. 124, 224501 (2006); M. M. Reif and P. H. Huenenberger, J. Chem. Phys. 134, 144103 (2010)], the application of appropriate correction terms permits to obtain methodology-independent results. The corrected values are then exclusively characteristic of the underlying molecular model including in particular the ion-solvent van der Waals interaction parameters, determining the effective ion size and the magnitude of its dispersion interactions. In the present study, the comparison of calculated (corrected) hydration free energies with experimental data (along with the consideration of ionic polarizabilities) is used to calibrate new sets of ion-solvent van der Waals (Lennard-Jones) interaction parameters for the alkali (Li{sup +}, Na{sup +}, K{sup +}, Rb{sup +}, Cs{sup +}) and halide (F{sup -}, Cl{sup -}, Br{sup -}, I{sup -}) ions along with either the SPC or the SPC/E water models. The experimental dataset is defined by conventional single-ion hydration free energies [Tissandier et al., J. Phys. Chem. A 102, 7787 (1998); Fawcett, J. Phys. Chem. B 103, 11181] along with three plausible choices for the (experimentally elusive) value of the absolute (intrinsic) hydration free energy of the proton, namely, {Delta}G{sub hyd} {sup O-minus} [H{sup +}]=-1100, -1075 or -1050 kJ mol{sup -1}, resulting in three sets L, M, and H for the SPC water model and three sets L{sub E}, M{sub E}, and H{sub E} for the SPC/E water model (alternative sets can easily be interpolated to intermediate {Delta}G{sub hyd} {sup O-minus} [H{sup +}] values). The residual sensitivity of the calculated (corrected) hydration free energies on the volume-pressure boundary conditions and on the effective

  11. Chloride, bromide and iodide scintillators with europium doping

    DOEpatents

    Zhuravleva, Mariya; Yang, Kan

    2014-08-26

    A halide scintillator material is disclosed where the halide may comprise chloride, bromide or iodide. The material is single-crystalline and has a composition of the general formula ABX.sub.3 where A is an alkali, B is an alkali earth and X is a halide which general composition was investigated. In particular, crystals of the formula ACa.sub.1-yEu.sub.yI.sub.3 where A=K, Rb and Cs were formed as well as crystals of the formula CsA.sub.1-yEu.sub.yX.sub.3 (where A=Ca, Sr, Ba, or a combination thereof and X=Cl, Br or I or a combination thereof) with divalent Europium doping where 0.ltoreq.y.ltoreq.1, and more particularly Eu doping has been studied at one to ten mol %. The disclosed scintillator materials are suitable for making scintillation detectors used in applications such as medical imaging and homeland security.

  12. Ionic conductivity studies in crystalline PVA/NaAlg polymer blend electrolyte doped with alkali salt KCl

    NASA Astrophysics Data System (ADS)

    Sheela, T.; Bhajantri, R. F.; Ravindrachary, V.; Pujari, P. K.; Rathod, Sunil G.; Naik, Jagadish

    2014-04-01

    Potassium Chloride (KCl) doped poly(vinyl alcohol) (PVA)/sodium alginate (NaAlg) in 60:40 wt% polymer blend electrolytes were prepared by solution casting method. The complexation of KCl with host PVA/NaAlg blend is confirmed by FTIR and UV-Vis spectra. The XRD studies show that the crystallinity of the prepared blends increases with increase in doping. The dc conductivity increases with increase in dopant concentration. Temperature dependent dc conductivity shows an Arrhenius behavior. The dielectric properties show that both the dielectric constant and dielectric loss increases with increase in KCl doping concentration and decreases with frequency. The cole-cole plots show a decrease in bulk resistance, indicates the increase in ac conductivity, due to increase in charge carrier mobility. The doping of KCl enhances the mechanical properties of PVA/NaAlg, such as Young's modulus, tensile strength, stiffness.

  13. Substantial enhancement in intrinsic coercivity on M-type strontium hexaferrite through the increase in magneto-crystalline anisotropy by co-doping of group-V and alkali elements

    SciTech Connect

    Ahn, Kyunghan Ryu, Byungki; Korolev, Dmitry; Jae Kang, Young

    2013-12-09

    The effect of d{sup 1} impurity doping in Sr-hexaferrite (SrM) on the magnetic anisotropy is investigated. First-principles calculations revealed that group-V elements (V, Nb) are stabilized with co-doping of alkali elements. Na{sup 1+}/K{sup 1+} doping at Sr{sup 2+}-site is found to be critical to form the d{sup 1} impurities at Fe-site. Experimentally, Na–V doped SrM shows the intrinsic coercivity of ∼5.4 kOe, which is ∼300% enhancement compared to undoped SrM and comparable value to La–Co co-doped SrM. Finally, the spin-orbit coupling from non-vanishing angular momentum of d{sup 1} impurity in SrM should be a main factor for such a substantial improvement of intrinsic coercivity.

  14. Role of glass structure in defining the chemical dissolution behavior, bioactivity and antioxidant properties of zinc and strontium co-doped alkali-free phosphosilicate glasses.

    PubMed

    Kapoor, Saurabh; Goel, Ashutosh; Tilocca, Antonio; Dhuna, Vikram; Bhatia, Gaurav; Dhuna, Kshitija; Ferreira, José M F

    2014-07-01

    We investigated the structure-property relationships in a series of alkali-free phosphosilicate glass compositions co-doped with Zn(2+) and Sr(2+). The emphasis was laid on understanding the structural role of Sr(2+) and Zn(2+) co-doping on the chemical dissolution behavior of glasses and its impact on their in vitro bioactivity. The structure of glasses was studied using molecular dynamics simulations in combination with solid state nuclear magnetic resonance spectroscopy. The relevant structural properties are then linked to the observed degradation behavior, in vitro bioactivity, osteoblast proliferation and oxidative stress levels. The apatite-forming ability of glasses has been investigated by X-ray diffraction, infrared spectroscopy and scanning electron microscopy-energy-dispersive spectroscopy after immersion of glass powders/bulk in simulated body fluid (SBF) for time durations varying between 1h and 14 days, while their chemical degradation has been studied in Tris-HCl in accordance with ISO 10993-14. All the glasses exhibit hydroxyapatite formation on their surface within 1-3h of their immersion in SBF. The cellular responses were observed in vitro on bulk glass samples using human osteosarcoma MG63 cell line. The dose-dependent cytoprotective effect of glasses with respect to the concentration of zinc and strontium released from the glasses is also discussed. PMID:24709542

  15. High Temperature Alkali Corrosion of Dense SN4 Coated with CMZP and Mg-Doped A21TiO5 in Coal Gas

    SciTech Connect

    J. J. Brown; Nguyen Thierry

    1997-10-01

    Si3N4 heat exchangers used in industrial systems are usually operating in harsh environments. Not only is this structural material experiencing high temperatures, but it is also subjected to corrosive gases and condensed phases. Past studies have demonstrated that condensed phases severely attack Si3N4 and as a consequence, dramatically reduce its lifetime in industrial operating systems.1,2 Previous research conducted at Virginia Tech on low thermal expansion coefficient oxide ceramics,3,4,5 (Ca1-X,MgX)Zr4(PO4)6 (CMZP), and Mg-doped Al2TiO5, for structural application have shown that these two materials exhibited better resistance to alkaline corrosion than Si3N4. Thus, they were envisioned as good candidates for a protective coating on Si3N4 heat exchangers. As a result, the goal of the present work is to develop CMZP and Mg-doped Al2TiO5 protective thin films using the sol-gel process and the dip coating technique and to test their effectiveness in an alkali-containing atmosphere.

  16. Optical properties and radiation damages of cerium fluoride crystals doped with alkali-earth and rare-earth elements

    SciTech Connect

    Gusev, Y.I.; Melchakov, E.N.; Mironov, I.A.; Panteleev, L.A.; Reiterov, V.M.; Rodnyi, P.A.; Seliverstov, D.M.; Shchetkowsky, A.I.; Yazikov, D.M.; Zakharov, N.G.

    1994-12-31

    The most essential contribution in the investigation of CeF{sub 3} crystals having the goal to construct high precision electromagnetic calorimeters has been done by Crystal Clear Collaboration. Study of optical properties and radiation damages of Cerium Fluoride crystals doped with Ca, Ba, Sr, La, Nd, Zr and Hf in the wide range of concentrations has been performed with the goal to obtain high optical transparency of crystals at different cumulative doses under {gamma}-irradiation. Time decay curves and relative light yields of scintillators as a function of doping level were measured using X-ray excitation of samples and single photon counting method.

  17. Dosimetric properties of new europium doped KBr phosphors

    NASA Astrophysics Data System (ADS)

    Bernal, R.; Tostado-García, W.; Alday-Samaniego, K. R.; Cruz-Vázquez, C.; Barboza-Flores, M.

    2003-03-01

    In this work, dosimetric properties of new sintered europium-doped KBr phosphors subjected to beta irradiation are investigated. The obtained results show that these phosphors exhibit promising thermoluminescence properties that made them a viable alternative to substitute the conventional alkali halides crystals of similar composition for dosimetric purposes, considering as important advantages the simplicity and economy of the fabrication. The thermoluminescence response shows a linear dose dependence up to order of some Grays, which is higher than the linearity presented by the crystals of similar composition. Also, the thermoluminiscence fading is stabilized faster than that of the crystals do.

  18. The Silver Halides

    ERIC Educational Resources Information Center

    Sahyun, M. R. V.

    1977-01-01

    Illustrates the type of fractional bonding for solid silver halides. Treats the silver halides as electron excess compounds, and develops a model of a localized bonding unit that may be iterated in three dimensions to describe the bulk phase. (MLH)

  19. Tug of war between AO-hybridization and aromaticity in dictating structures of Li-doped alkali clusters

    NASA Astrophysics Data System (ADS)

    Alexandrova, Anastassia N.

    2012-04-01

    Hybridization of atomic orbitals is a widely appreciated phenomenon in organic chemistry. Here, we demonstrate that hybridization also can dramatically impact the shapes of small all-alkali metal clusters, and oppose σ-aromaticity in defining cluster shapes. The valence-iso-electronic LiNa4- and LiK4- clusters adopt different global minimum structures: LiNa4- is a planar C2v (1A1) species distorted from the perfect pentagon, and LiK4- is a planar square D4h (1A1g) species with Li being in the centre. This effect is rooted in the different degrees of the 2s-2p hybridization in Li in response to binding to Na versus K.

  20. Unified picture of the doping dependence of superconducting transition temperatures in alkali metal/ammonia intercalated FeSe

    NASA Astrophysics Data System (ADS)

    Guterding, Daniel; Jeschke, Harald O.; Hirschfeld, P. J.; Valentí, Roser

    2015-01-01

    In the recently synthesized Lix(NH2)y(NH3)zFe2Se2 family of iron chalcogenides, a molecular spacer consisting of lithium ions, lithium amide, and ammonia separates the layers of FeSe. It has been shown that upon variation of the chemical composition of the spacer layer, superconducting transition temperatures can reach Tc˜44 K , but the relative importance of the layer separation and effective doping to the Tc enhancement is currently unclear. Using state of the art band structure unfolding techniques, we construct eight-orbital models from ab initio density functional theory calculations for these materials. Within an RPA spin-fluctuation approach, we show that the electron doping enhances the superconducting pairing, which is of s± symmetry and explain the experimentally observed limit to Tc in the molecular spacer intercalated FeSe class of materials.

  1. Metal-halide mixtures for latent heat energy storage

    NASA Technical Reports Server (NTRS)

    Chen, K.; Manvi, R.

    1981-01-01

    Alkali metal and alkali halide mixtures are identified which may be suitable for thermal energy storage at temperatures above 600 C. The use of metal-halides is appropriate because of their tendency to form two immiscible melts with a density difference, which reduces scale formation and solidification on heat transfer surfaces. Also, the accumulation of phase change material along the melt interface is avoided by the self-dispersing characteristic of some metal-halides, in particular Sr-SrCl2, Ba-BaCl2, and Ba-BaBr2 mixtures. Further advantages lie in their high thermal conductivities, ability to cope with thermal shock, corrosion inhibition, and possibly higher energy densities.

  2. Research on the correlation between the optical gap and chemical bond in sulphur and selenium co-doped chalco-halide glasses.

    PubMed

    Zhu, Mingxing; Nie, Qiuhua; Wang, Xunsi; Dai, Shixun; Zhang, Xianghua; Shen, Xiang; Wang, Guoxiang; Lv, Xin

    2010-04-01

    The Ge-Ga-Se-S-CsCl glasses were prepared by the melting-quenching method. The absorption and transmission spectrum were measured under room temperature. It is found that these glasses have high broad spectral range of transparency from visible to far-infrared region (0.4-12 microm). The relationship between the optical gap and chemical composition in terms of novel chalco-halide glasses is discussed based on the Pauling's theory model, which is using the modified heats of atomization and the coordination number of the elements, to explain this phenomena for the first time. PMID:20096623

  3. Ion Size Effect on Glow Peak Temperature in Dielectric Binary Mixed Crystals Doped With Divalent Europium

    NASA Astrophysics Data System (ADS)

    Rodriguez-Mijangos, Ricardo; Perez-Salas, Raul

    2008-03-01

    Thermoluminiscence measurements at room temperature of ``beta'' irradiated divalent Europium doped binary mixed alkali halides with RbCl and KBr components at several concentrations x in molar fraction are carried out. The experiments have been carried out to identify the effect of composition in thermoluminiscense glow peaks. A typical glow peak has been distinguished for each composition. A linear dependence of its temperature on the composition x has been found. This is principally associated with the radii size change of halogen ions. Comparison with results in mixed KCl:KBr. KBr:RbBr and KCl:RbCl support that assertion.

  4. Alkali Bee

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The alkali bee, Nomia melanderi, is native to deserts and semi-arid desert basins of the western United States. It is a very effective and manageable pollinator for the production of seed in alfalfa (=lucerne) and some other crops, such as onion. It is the world’s only intensively managed ground-n...

  5. Nonmagnetic 2p-block elements (B, C, N, and O)-doped AgCl for potential halide spintronic applications: A first-principles perspective

    NASA Astrophysics Data System (ADS)

    Lu, Yi-Lin; Dong, Shengjie; Zhou, Wei; Zhao, Hui; Wu, Ping

    2016-08-01

    The structural, electronic, and magnetic properties of 2p-block non-metallic elements (B, C, N, and O)-doped silver chloride were investigated by using ab initio approaches. The results indicate that B, C, N, and O substitution can produce magnetism and the magnetization is mainly from the 2p component of the 2p-block impurities. The total magnetic moments are 2.00, 3.00, 2.00, and 0.98 μB per 2 × 2 × 2 supercell for B, C, N, and O doping, respectively. Semiconducting, half-metallic, and nearly half-metallic magnetic states were generally observed in these cases. The ferromagnetic coupling was observed for B-, N-, and O-doped samples except for C-doped model. Thus, although the calculated magnetic moment of C-doped AgCl is 3.00 μB, the total net magnetic moment should be zero due to the antiferromagnetic order. Several possible explanations have been rationalized from the diversification of the electron count, the hole-mediated p- p and p- d interactions' coupling mechanisms, the elements' electronegativity and the relationship between guest and host atoms.

  6. Effect of MoO3 on electron paramagnetic resonance spectra, optical spectra and dc conductivity of vanadyl ion doped alkali molybdo-borate glasses

    NASA Astrophysics Data System (ADS)

    Agarwal, A.; Khasa, S.; Seth, V. P.; Sanghi, S.; Arora, M.

    2014-02-01

    Alkali molybdo-borate glasses having composition xMoO3·(30 - x)M2O·70B2O3 and xMoO3·(70 - x)B2O3·30M2O (M = Li, Na, K) with 0 ⩽ x ⩽ 15 (mol%) doped with 2.0 mol% of V2O5 have been prepared in order to study the influence of MoO3 on electrical conductivity, electron paramagnetic resonance (EPR) and optical spectra. From EPR studies it is observed that V4+ ions in these samples exist as VO2+ ions in octahedral coordination with a tetragonal compression and belong to C4V symmetry. The tetragonal nature and octahedral symmetry of V4+O6 complex increase as well as decrease depending upon the composition of glasses with increase in MoO3 but 3dxy orbit of unpaired electron in the VO2+ ion expands in all the glasses. The decrease in optical band gap suggests that there is an increase in the concentration of non-bridging oxygen's. From the study of optical transmission spectra it is observed that for all the glasses the degree of covalency of the σ-bonding decreases with increase in MoO3 content and the degree of covalency of the π-bonding also varies. These results based on optical spectroscopy are in agreement with EPR findings. It is found that dc conductivity decreases and activation energy increases with increase in MoO3:M2O (M = Li, Na, K) ratio in MoO3·M2O·B2O3 glasses, whereas the conductivity increases and activation energy decreases with increase in MoO3:B2O3 ratio in xMoO3·B2O3·M2O glasses, which is governed by the increase in nonbridging oxygen's. The variation in theoretical optical basicity, Λth is also studied.

  7. Oxidation of hydrogen halides to elemental halogens with catalytic molten salt mixtures

    DOEpatents

    Rohrmann, Charles A.

    1978-01-01

    A process for oxidizing hydrogen halides by means of a catalytically active molten salt is disclosed. The subject hydrogen halide is contacted with a molten salt containing an oxygen compound of vanadium and alkali metal sulfates and pyrosulfates to produce an effluent gas stream rich in the elemental halogen. The reduced vanadium which remains after this contacting is regenerated to the active higher valence state by contacting the spent molten salt with a stream of oxygen-bearing gas.

  8. Metal-halide mixtures for latent heat energy storage

    NASA Technical Reports Server (NTRS)

    Chen, K.; Manvi, R.

    1981-01-01

    Some candidates for alkali metal and alkali halide mixtures suitable for thermal energy storage at temperatures 600 C are identified. A solar thermal system application which offer advantages such as precipitation of salt crystals away from heat transfer surfaces, increased thermal conductivity of phase change materials, corrosion inhibition, and a constant monotectic temperature, independent of mixture concentrations. By using the lighters, metal rich phase as a heat transfer medium and the denser, salt rich phase as a phase change material for latent heat storage, undesirable solidification on the heat transfer surface may be prevented, is presented.

  9. Bio-conventional bleaching of kadam kraft-AQ pulp by thermo-alkali-tolerant xylanases from two strains of Coprinellus disseminatus for extenuating adsorbable organic halides and improving strength with optical properties and energy conservation.

    PubMed

    Lal, Mohan; Dutt, Dharm; Tyagi, C H

    2012-04-01

    Two novel thermo-alkali-tolerant crude xylanases namely MLK-01 (enzyme-A) and MLK-07 (enzyme-B) from Coprinellus disseminatus mitigated kappa numbers of Anthocephalus cadamba kraft-AQ pulps by 32.5 and 34.38%, improved brightness by 1.5 and 1.6% and viscosity by 5.75 and 6.47% after (A)XE(1) and (B)XE(1)-stages, respectively. The release of reducing sugars and chromophores was the highest during prebleaching of A. cadamba kraft-AQ pulp at enzyme doses of 5 and 10 IU/g, reaction times 90 and 120 min, reaction temperatures 75 and 65°C and consistency 10% for MLK-01 and MLK-07, respectively. MLK-07 was more efficient than MLK01 in terms of producing pulp brightness, improving mechanical strength properties and reducing pollution load. MLK-01 and MLK-07 reduced AOX by 19.51 and 42.77%, respectively at 4% chlorine demands with an increase in COD and colour due to removal of lignin carbohydrates complexes. A. cadamba kraft-AQ pulps treated with xylanases from MLK-01 to MLK-07 and followed by CEHH bleaching at half chlorine demand (2%) showed a drastic reduction in brightness with slight improvement in mechanical strength properties compared to pulp bleached at 4% chlorine demand. MLK-01 reduced AOX, COD and colour by 43.83, 39.03 and 27.71% and MLK-07 by 38.34, 40.48 and 30.77%, respectively at half chlorine demand compared to full chlorine demand (4%). pH variation during prebleaching of A. cadamba kraft-AQ pulps with strains MLK-01 and MLK-07 followed by CEHH bleaching sequences showed a decrease in pulp brightness, AOX, COD and colour with an increase in mechanical strength properties, pulp viscosity and PFI revolutions to get a beating level of 35 ± 1 °SR at full chlorine demand. PMID:22805918

  10. Vitrification of IFR and MSBR halide salt reprocessing wastes

    SciTech Connect

    Siemer, D.D.

    2013-07-01

    Both of the genuinely sustainable (breeder) nuclear fuel cycles (IFR - Integral Fast Reactor - and MSBR - Molten Salt Breeder Reactor -) studied by the USA's national laboratories would generate high level reprocessing waste (HLRW) streams consisting of a relatively small amount ( about 4 mole %) of fission product halide (chloride or fluoride) salts in a matrix comprised primarily (about 95 mole %) of non radioactive alkali metal halide salts. Because leach resistant glasses cannot accommodate much of any of the halides, most of the treatment scenarios previously envisioned for such HLRW have assumed a monolithic waste form comprised of a synthetic analog of an insoluble crystalline halide mineral. In practice, this translates to making a 'substituted' sodalite ('Ceramic Waste Form') of the IFR's chloride salt-based wastes and fluoroapatite of the MSBR's fluoride salt-based wastes. This paper discusses my experimental studies of an alternative waste management scenario for both fuel cycles that would separate/recycle the waste's halide and immobilize everything else in iron phosphate (Fe-P) glass. It will describe both how the work was done and what its results indicate about how a treatment process for both of those wastes should be implemented (fluoride and chloride behave differently). In either case, this scenario's primary advantages include much higher waste loadings, much lower overall cost, and the generation of a product (glass) that is more consistent with current waste management practices. (author)

  11. Process for oxidation of hydrogen halides to elemental halogens

    DOEpatents

    Lyke, Stephen E.

    1992-01-01

    An improved process for generating an elemental halogen selected from chlorine, bromine or iodine, from a corresponding hydrogen halide by absorbing a molten salt mixture, which includes sulfur, alkali metals and oxygen with a sulfur to metal molar ratio between 0.9 and 1.1 and includes a dissolved oxygen compound capable of reacting with hydrogen halide to produce elemental halogen, into a porous, relatively inert substrate to produce a substrate-supported salt mixture. Thereafter, the substrate-supported salt mixture is contacted (stage 1) with a hydrogen halide while maintaining the substrate-supported salt mixture during the contacting at an elevated temperature sufficient to sustain a reaction between the oxygen compound and the hydrogen halide to produce a gaseous elemental halogen product. This is followed by purging the substrate-supported salt mixture with steam (stage 2) thereby recovering any unreacted hydrogen halide and additional elemental halogen for recycle to stage 1. The dissolved oxygen compound is regenerated in a high temperature (stage 3) and an optical intermediate temperature stage (stage 4) by contacting the substrate-supported salt mixture with a gas containing oxygen whereby the dissolved oxygen compound in the substrate-supported salt mixture is regenerated by being oxidized to a higher valence state.

  12. Ion Size Effect in Glow Peak Temperature in Binary Mixed Crystals Doped with Divalente Europium

    NASA Astrophysics Data System (ADS)

    Rodriguez-Mijangos, Ricardo; Perez-Salas, Raul

    2006-03-01

    Thermoluminiscence measurements at room temperature of ``beta'' irradiated divalent Europium doped binary mixed alkali halides with KCl and KBr components at several concentrations x in molar fraction. The experiments have been carried out to identify the effect of composition of glow peaks. A typical glow peak has been distinguished for each composition. A linear dependence of its temperature on the composition x has been found. This is associated with the size change of ions Cl and Br. Initial comparative cathodoluminiscent measurement was carried out irradiating a single sample with electrons in an electron microscopy using a 30 KV voltage. With the present results is speculated the behavior of the mixed binary crystals with components KCl and RbCl, doped with divalent Europium.

  13. Cold ablation driven by localized forces in alkali halides.

    PubMed

    Hada, Masaki; Zhang, Dongfang; Pichugin, Kostyantyn; Hirscht, Julian; Kochman, Michał A; Hayes, Stuart A; Manz, Stephanie; Gengler, Regis Y N; Wann, Derek A; Seki, Toshio; Moriena, Gustavo; Morrison, Carole A; Matsuo, Jiro; Sciaini, Germán; Miller, R J Dwayne

    2014-01-01

    Laser ablation has been widely used for a variety of applications. Since the mechanisms for ablation are strongly dependent on the photoexcitation level, so called cold material processing has relied on the use of high-peak-power laser fluences for which nonthermal processes become dominant; often reaching the universal threshold for plasma formation of ~1 J cm(-2) in most solids. Here we show single-shot time-resolved femtosecond electron diffraction, femtosecond optical reflectivity and ion detection experiments to study the evolution of the ablation process that follows femtosecond 400 nm laser excitation in crystalline sodium chloride, caesium iodide and potassium iodide. The phenomenon in this class of materials occurs well below the threshold for plasma formation and even below the melting point. The results reveal fast electronic and localized structural changes that lead to the ejection of particulates and the formation of micron-deep craters, reflecting the very nature of the strong repulsive forces at play. PMID:24835317

  14. Calculations of hyper-Raman tensor components of alkali halides

    NASA Astrophysics Data System (ADS)

    de Landa Castillo-Alvarado, Fray; Kucharczyk, Wlotek

    1998-03-01

    Calculations of hyper-Raman tensor components of NaCl,KCl and KBr crystals based on the bond polizability approach are presented. The results obtained are in good agreement whit experimental data reported previously in literature. A week cubic anisotropy of the hyper-Raman tensor is found. For LO mode our results predict the lattice deformation contribution to hyper-Raman scattering to be comparable whit the electro-optic contribution.

  15. Calculations of hyper-Raman tensor components of alkali halides

    NASA Astrophysics Data System (ADS)

    Kucharczyk, W.; Castillo Alvarado, F. L.

    1999-01-01

    Calculations of hyper-Raman scattering by the zone-centre optical phonons in NaCl, KCl and KBr crystals based on the bond polarizability approach are presented. The results obtained for the hyper-Raman tensor components are in agreement with experimental data reported previously in literature. A weak cubic anisotropy of the hyper-Raman tensor is found. For the LO mode our results predict the lattice and electro-optic contributions to hyper-Raman scattering to be of the same order of magnitude.

  16. Formation of Na2SO4 and K2SO4 in flames doped with sulfur and alkali chlorides and carbonates

    NASA Technical Reports Server (NTRS)

    Fryburg, G. C.; Miller, R. A.; Stearns, C. A.; Kohl, F. J.

    1977-01-01

    High pressure, free-jet expansion, mass spectrometric sampling was used to identify directly and to measure reaction products formed in doped methane-oxygen flames. Flames were doped with SO2 or CH3SH and sodium or potassium chlorides or carbonates. Gaseous NA2SO4 or K2S04 molecules were formed in residence times on the order of msec for each combination of dopants used. Composition profiles of combustion products were measured and compared with equilibrium thermodynamic calculations of product composition.

  17. Formation of Na2SO4 and K2SO4 in flames doped with sulfur and alkali chlorides and carbonates

    NASA Technical Reports Server (NTRS)

    Fryburg, G. C.; Miller, R. A.; Stearns, C. A.; Kohl, F. J.

    1977-01-01

    High pressure, free-jet expansion, mass spectrometric sampling was used to identify directly and to measure reaction products formed in doped methane-oxygen flames. Flames were doped with SO2 or CH3SH and sodium or potassium chlorides or carbonates. Gaseous Na2SO4 or K2SO4 molecules were formed in residence times on the order of 1 msec for each combination of dopants used. Composition profiles of combustion products were measured and compared with equilibrium thermodynamic calculations of product composition.

  18. Alkali metal nitrate purification

    DOEpatents

    Fiorucci, Louis C.; Morgan, Michael J.

    1986-02-04

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

  19. High Biomass Specific Methyl Halide Production Rates of Selected Coastal Marsh Plants and its Relationship to Halide Content

    NASA Astrophysics Data System (ADS)

    Manley, S. L.; Wang, N.; Cicerone, R. J.

    2002-12-01

    Salt tolerant coastal marsh plants (halophytes) have previously been shown to be globally significant producers of methyl chloride (MeCl) and methyl bromide (MeBr). While halophytes are known for their high salt content, there are few reports of their halide content. Our studies have attempted to quantify biomass specific methyl halide (MeX) production from these plants and relate it to tissue halide levels. MeCl, MeBr and MeI production rates and tissue chloride, bromide and iodide concentrations from selected coastal marsh plants were measured for nearly a year. Certain halophyte species (i.e. Batis and Frankenia) have very high summer biomass specific production rates for MeX (e.g. Frankenia: 1 ug MeCl /gfwt/hr; 80 ng MeBr/gfwt/hr; 8 ng MeI/gfwt/hr). These rates of MeCl and MeBr production are much higher than those from other coastal marsh plants or seaweeds. Plant halide levels remain high throughout the year, while MeX production peaks at a high level in mid summer falling to low winter rates. This implies a linkage to plant growth. Higher levels of chloride and bromide were seen in the fleshy marsh plants such as Batis (saltwort, approximately 20 percent dry wt chloride, 0.4 percent dry wt bromide) and Salicornia (pickleweed) than in the others such as Frankenia (alkali heath) approx 7 percent dry wt chloride, 0.1 percent dry wt bromide) or Spartina (cordgrass). No such trend was seen for iodide, which ranged from 4 - 10 ppm. Calculations show the daily halide losses from MeX production are far less than the variability in tissue halide content. MeX production removes a small fraction of the total tissue halide from these plants suggesting that MeX production is not a mechanism used by these species to control internal halide levels. Saltwort cell-free extracts incubated with bromide or iodide in the presence of S-adenosyl-L-methionine (SAM) produced the corresponding MeX. MeBr production was inhibited by caffeic acid the substrate of lignin-specific O

  20. Milk-alkali syndrome

    MedlinePlus

    ... 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 ...

  1. First-principles computational studies of alkali-doped C60 fullerides. Final technical report, 1 Jan 91-1 Jan 92

    SciTech Connect

    Erwin, S.C.

    1992-04-06

    Researchers at AT and T Bell Laboratories reported the discovery of superconductivity at 18 K in a potassium-doped fullerene solid, KxC60. This marked a major turning point in the young history of the C60 molecule 'buckminsterfullerene': from a hypothetical molecular (1985), to small-scale (mg) production of crystalline powders (1988), to large-scale synthesis (1990), to a material with the highest transition temperature of any molecular superconductor. This history represents only one of many research lines. Concurrently with the work at AT and T on partial doping, researchers at the Laboratory for Research on the Structure of Matter at the University of Pennsylvania were doping solid C60 to saturation with potassium. The resulting pure phase, K6C60, was characterized by x-ray diffraction in April 1991: the lattice was body-centered cubic, with the C60 molecules essentially undistorted, orientationally ordered, and each surrounded by a cage of 24 K atoms. Nothing was known about the electronic structure at this early stage.

  2. PREPARATION OF HALIDES OF PLUTONIUM

    DOEpatents

    Garner, C.S.; Johns, I.B.

    1958-09-01

    A dry chemical method is described for preparing plutonium halides, which consists in contacting plutonyl nitrate with dry gaseous HCl or HF at an elevated temperature. The addition to the reaction gas of a small quantity of an oxidizing gas or a reducing gas will cause formation of the tetra- or tri-halide of plutonium as desired.

  3. Halide laser glasses

    SciTech Connect

    Weber, M.J.

    1982-01-14

    Energy storage and energy extraction are of prime importance for efficient laser action and are affected by the line strengths and linewidths of optical transitions, excited-state lifetimes, nonradiative decay processes, spectroscopic inhomogeneities, nonlinear refractive index, and damage threshold. These properties are all host dependent. To illustrate this, the spectroscopic properties of Nd/sup 3 +/ have been measured in numerous oxide, oxyhalide, and halide glasses. A table summarizes the reported ranges of stimulated emission cross sections, peak wavelengths, linewidths, and radiative lifetimes associated with the /sup 4/F/sub 3/2/ ..-->.. /sup 4/I/sub 11/2/ lasing transition.

  4. Ion Partitioning at the liquid/vapor interface of a multi-component alkali halidesolution: A model for aqueous sea salt aerosols

    SciTech Connect

    Ghosal, Sutapa; Brown, Matthew A.; Bluhm, Hendrik; Krisch, Maria J.; Salmeron, Miquel; Jungwirth, Pavel; Hemminger, John C.

    2008-12-22

    The chemistry of Br species associated with sea salt ice and aerosols has been implicated in the episodes of ozone depletion reported at Arctic sunrise. However, Br{sup -} is only a minor component in sea salt, which has a Br{sup -}/Cl{sup -} molar ratio of {approx}0.0015. Sea salt is a complex mixture of many different species, with NaCl as the primary component. In recent years experimental and theoretical studies have reported enhancement of the large, more polarizable halide ion at the liquid/vapor interface of corresponding aqueous alkali halide solutions. The proposed enhancement is likely to influence the availability of sea salt Br{sup -} for heterogeneous reactions such as those involved in the ozone depletion episodes. We report here ambient pressure x-ray photoelectron spectroscopy studies and molecular dynamics simulations showing direct evidence of Br{sup -} enhancement at the interface of an aqueous NaCl solution doped with bromide. The experiments were carried out on samples with Br{sup -}/Cl{sup -} ratios in the range 0.1% to 10%, the latter being also the ratio for which simulations were carried out. This is the first direct measurement of interfacial enhancement of Br{sup -} in a multi-component solution with particular relevance to sea salt chemistry.

  5. Suppression of nonradiative recombination in ionic insulators by defects: Role of fast electron trapping in Tl-doped CsI

    SciTech Connect

    Bang, Junhyeok; Wang, Zheming; Gao, Fei; Meng, Sheng; Zhang, Shengbai

    2013-05-23

    In semiconductors, defects often assist non-radiative relaxation. However, Tl doping can significantly suppress the non-radiative relaxation in alkali halides to increase scintillation efficiency. Without the Tl, it is known that the creation of Frenkel pairs at self-trapped excitons, assisted by excited electron and hole relaxations, is the reason for the non-radiative relaxation. Here we show by first-principles calculation that Tl doping introduces Tl p states inside the band gap to trap the excited electrons. The trapping is highly effective to within several ps, as revealed by time-dependent density functional theory calculations. It alters the non-radiative relaxation process to result in a noticeable increase in the relaxation barrier from 0.3 to 0.63 eV, which reduces the non-radiative relaxation by roughly a factor of 105 at room temperature.

  6. Passive particle dosimetry. [silver halide crystal growth

    NASA Technical Reports Server (NTRS)

    Childs, C. B.

    1977-01-01

    Present methods of dosimetry are reviewed with emphasis on the processes using silver chloride crystals for ionizing particle dosimetry. Differences between the ability of various crystals to record ionizing particle paths are directly related to impurities in the range of a few ppm (parts per million). To understand the roles of these impurities in the process, a method for consistent production of high purity silver chloride, and silver bromide was developed which yields silver halides with detectable impurity content less than 1 ppm. This high purity silver chloride was used in growing crystals with controlled doping. Crystals were grown by both the Czochalski method and the Bridgman method, and the Bridgman grown crystals were used for the experiments discussed. The distribution coefficients of ten divalent cations were determined for the Bridgman crystals. The best dosimeters were made with silver chloride crystals containing 5 to 10 ppm of lead; other impurities tested did not produce proper dosimeters.

  7. Structural models for alkali-metal complexes of polyacetylene

    NASA Astrophysics Data System (ADS)

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

    1990-02-01

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

  8. Electron thermalization and trapping rates in pure and doped alkali and alkaline-earth iodide crystals studied by picosecond optical absorption

    NASA Astrophysics Data System (ADS)

    Ucer, K. B.; Bizarri, G.; Burger, A.; Gektin, A.; Trefilova, L.; Williams, R. T.

    2014-04-01

    Although light continues to be emitted from insulating crystals used as scintillators over a period of nanoseconds to microseconds after stopping of an energetic particle, much of what determines the nonlinearity of response goes on in the first picoseconds. On this time scale, free carriers and excitons are at high density near the track core and thus are subject to nonlinear quenching. The hot (free) electrons eventually cool to low enough energy that trapping on holes, dopants, or defects can commence. In the track environment, spatial distributions of trapped carriers determined on the picosecond time scale can influence the proportionality between light yield and the initial particle energy throughout the whole light pulse. Picosecond spectroscopy of optical absorption induced by a short pulse of above-gap excitation provides a useful window on what occurs during the crucial early evolution of excited populations. The laser excitation can be tuned to excite carriers that are initially very hot (˜3 eV) relative to the band edges, or that are almost thermalized (˜0.1 eV excess energy) at the outset. Undoped and doped samples of NaI:Tl(0%, 0.1%), CsI:Tl(0%, 0.01%, 0.04%, 0.3%), and SrI2:Eu(0%, 0.2%, 0.5%, 3%) are studied in this work.

  9. METHOD OF PREPARING METAL HALIDES

    DOEpatents

    Hendrickson, A.V.

    1958-11-18

    The conversion of plutonium halides from plutonium peroxide can be done by washing the peroxide with hydrogen peroxide, drying the peroxide, passing a dry gaseous hydrohalide over the surface of the peroxide at a temperature of about lOO icient laborato C until the reaction rate has stabillzed, and then ralsing the reaction temperature to between 400 and 600 icient laborato C until the conversion to plutonium halide is substantially complete.

  10. Actinide halide complexes

    DOEpatents

    Avens, L.R.; Zwick, B.D.; Sattelberger, A.P.; Clark, D.L.; Watkin, J.G.

    1992-11-24

    A compound is described of the formula MX[sub n]L[sub m] wherein M is a metal atom selected from the group consisting of thorium, plutonium, neptunium or americium, X is a halide atom, n is an integer selected from the group of three or four, L is a coordinating ligand selected from the group consisting of aprotic Lewis bases having an oxygen-, nitrogen-, sulfur-, or phosphorus-donor, and m is an integer selected from the group of three or four for monodentate ligands or is the integer two for bidentate ligands, where the sum of n+m equals seven or eight for monodentate ligands or five or six for bidentate ligands. A compound of the formula MX[sub n] wherein M, X, and n are as previously defined, and a process of preparing such actinide metal compounds are described including admixing the actinide metal in an aprotic Lewis base as a coordinating solvent in the presence of a halogen-containing oxidant.

  11. Actinide halide complexes

    DOEpatents

    Avens, Larry R.; Zwick, Bill D.; Sattelberger, Alfred P.; Clark, David L.; Watkin, John G.

    1992-01-01

    A compound of the formula MX.sub.n L.sub.m wherein M is a metal atom selected from the group consisting of thorium, plutonium, neptunium or americium, X is a halide atom, n is an integer selected from the group of three or four, L is a coordinating ligand selected from the group consisting of aprotic Lewis bases having an oxygen-, nitrogen-, sulfur-, or phosphorus-donor, and m is an integer selected from the group of three or four for monodentate ligands or is the integer two for bidentate ligands, where the sum of n+m equals seven or eight for monodentate ligands or five or six for bidentate ligands, a compound of the formula MX.sub.n wherein M, X, and n are as previously defined, and a process of preparing such actinide metal compounds including admixing the actinide metal in an aprotic Lewis base as a coordinating solvent in the presence of a halogen-containing oxidant, are provided.

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

    SciTech Connect

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

    2012-07-01

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

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

    SciTech Connect

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

    2012-07-01

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

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

    SciTech Connect

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

    1980-02-26

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

  15. Radiochemical synthesis of pure anhydrous metal halides

    NASA Technical Reports Server (NTRS)

    Philipp, W. H.; Marsik, S. J.; May, C. E.

    1973-01-01

    Method uses radiation chemistry as practical tool for inorganic preparations and in particular deposition of metals by irradiation of their aqueous metal salt solutions with high energy electrons. Higher valence metal halide is dissolved in organic liquid and exposed to high energy electrons. This causes metal halide to be reduced to a lower valence metal halide.

  16. Preparation of cerium halide solvate complexes

    DOEpatents

    Vasudevan, Kalyan V; Smith, Nickolaus A; Gordon, John C; McKigney, Edward A; Muenchaussen, Ross E

    2013-08-06

    Crystals of a solvated cerium(III) halide solvate complex resulted from a process of forming a paste of a cerium(III) halide in an ionic liquid, adding a solvent to the paste, removing any undissolved solid, and then cooling the liquid phase. Diffusing a solvent vapor into the liquid phase also resulted in crystals of a solvated cerium(III) halide complex.

  17. Optical Properties of Tm(3+) Ions in Alkali Germanate Glass

    NASA Technical Reports Server (NTRS)

    Walsh, Brian M.; Barnes, Norman P.; Reichle, Donald J.; Jiang, Shibin

    2006-01-01

    Tm-doped alkali germanate glass is investigated for use as a laser material. Spectroscopic investigations of bulk Tm-doped germanate glass are reported for the absorption, emission and luminescence decay. Tm:germanate shows promise as a fiber laser when pumped with 0.792 m diodes because of low phonon energies. Spectroscopic analysis indicates low nonradiative quenching and pulsed laser performance studies confirm this prediction by showing a quantum efficiency of 1.69.

  18. Alkali metal ionization detector

    DOEpatents

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

    1978-01-01

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

  19. Optical properties of lanthanide-containing halide-modified zinc tellurite glasses

    SciTech Connect

    Sidebottom, D.L.; Hruschka, M.A.; Potter, B.G.; Brow, R.K.; Hudgens, J.J.

    1996-12-31

    As part of an ongoing investigation to characterize the properties and structure of Zn halide-Te oxide glasses, we report preliminary measurements of the optical properties of several Nd- and Er-doped tellurites. Measurements include fluorescence lifetimes and estimates of the theoretical radiative lifetimes (from traditional Judd-Ofelt analysis of optical absorption spectra) as well as phonon sideband studies sensitive to vibrational characteristics near the rare earth ion. Response of these optical features to the substitution of alternative halides is examined.

  20. Atomic forces between noble gas atoms, alkali ions, and halogen ions for surface interactions

    NASA Technical Reports Server (NTRS)

    Wilson, J. W.; Outlaw, R. A.; Heinbockel, J. H.

    1988-01-01

    The components of the physical forces between noble gas atoms, alkali ions, and halogen ions are analyzed and a data base developed from analysis of the two-body potential data, the alkali-halide molecular data, and the noble gas crystal and salt crystal data. A satisfactory global fit to this molecular and crystal data is then reproduced by the model to within several percent. Surface potentials are evaluated for noble gas atoms on noble gas surfaces and salt crystal surfaces with surface tension neglected. Within this context, the noble gas surface potentials on noble gas and salt crystals are considered to be accurate to within several percent.

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

    NASA Technical Reports Server (NTRS)

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

    1966-01-01

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

  2. Development of Halide and Oxy-Halides for Isotopic Separations

    SciTech Connect

    Leigh R. Martin; Aaron T. Johnson; Jana Pfeiffer; Martha R. Finck

    2014-10-01

    The goal of this project was to synthesize a volatile form of Np for introduction into mass spectrometers at INL. Volatile solids of the 5f elements are typically those of the halides (e.g. UF6), however fluorine is highly corrosive to the sensitive internal components of the mass separator, and the other volatile halides exist as several different stable isotopes in nature. However, iodide is both mono-isotopic and volatile, and as such presents an avenue for creation of a form of Np suitable for introduction into the mass separator. To accomplish this goal, the technical work in the project sought to establish a novel synthetic route for the conversion NpO2+ (dissolved in nitric acid) to NpI3 and NpI4.

  3. Alkalis and Skin.

    PubMed

    Greenwood, John E; Tan, Jin Lin; Ming, Justin Choong Tzen; Abell, Andrew D

    2016-01-01

    The aim of this editorial is to provide an overview of the chemical interactions occurring in the skin of our patients on contact with alkaline agents. Strongly basic alkali is highly aggressive and will readily hydrolyze (or cleave) key biological molecules such as lipids and proteins. This phenomenon is known as saponification in the case of lipids and liquefactive denaturation for peptides and proteins. A short section on current first-aid concepts is included. A better understanding of the basic science behind alkali burns will make us better teachers and provide an insight into the urgency needed in treating these common and dangerous chemical injuries. PMID:26182072

  4. Alkali metal ion battery with bimetallic electrode

    SciTech Connect

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

    2015-04-07

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

  5. Methods of recovering alkali metals

    DOEpatents

    Krumhansl, James L; Rigali, Mark J

    2014-03-04

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

  6. Charge carrier mobility in hybrid halide perovskites

    PubMed Central

    Motta, Carlo; El-Mellouhi, Fedwa; Sanvito, Stefano

    2015-01-01

    The charge transport properties of hybrid halide perovskites are investigated with a combination of density functional theory including van der Waals interaction and the Boltzmann theory for diffusive transport in the relaxation time approximation. We find the mobility of electrons to be in the range 5–10 cm2V−1s−1 and that for holes within 1–5 cm2V−1s−1, where the variations depend on the crystal structure investigated and the level of doping. Such results, in good agreement with recent experiments, set the relaxation time to about 1 ps, which is the time-scale for the molecular rotation at room temperature. For the room temperature tetragonal phase we explore two possible orientations of the organic cations and find that the mobility has a significant asymmetry depending on the direction of the current with respect to the molecular axis. This is due mostly to the way the PbI3 octahedral symmetry is broken. Interestingly we find that substituting I with Cl has minor effects on the mobilities. Our analysis suggests that the carrier mobility is probably not a key factor in determining the high solar-harvesting efficiency of this class of materials. PMID:26235910

  7. 40 CFR 721.4095 - Quaternary ammonium alkyltherpropyl trialkylamine halides.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... trialkylamine halides. 721.4095 Section 721.4095 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4095 Quaternary ammonium alkyltherpropyl trialkylamine halides. (a... generically as quaternary ammonium alkyltherpropyl trialkylamine halides (PMNs...

  8. TRANSURANIC METAL HALIDES AND A PROCESS FOR THE PRODUCTION THEREOF

    DOEpatents

    Fried, S.

    1951-03-20

    Halides of transuranic elements are prepared by contacting with aluminum and a halogen, or with an aluminum halide, a transuranic metal oxide, oxyhalide, halide, or mixture thereof at an elevated temperature.

  9. Chlor-Alkali Technology.

    ERIC Educational Resources Information Center

    Venkatesh, S.; Tilak, B. V.

    1983-01-01

    Chlor-alkali technology is one of the largest electrochemical industries in the world, the main products being chlorine and caustic soda (sodium hydroxide) generated simultaneously by the electrolysis of sodium chloride. This technology is reviewed in terms of electrochemical principles and manufacturing processes involved. (Author/JN)

  10. Hydrothermal alkali metal recovery process

    DOEpatents

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

    1980-01-01

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

  11. Simple model potential and model wave functions for (H-alkali)+ and (alkali-alkali)+ ions

    NASA Astrophysics Data System (ADS)

    Patil, S. H.; Tang, K. T.

    2000-07-01

    A simple model potential is proposed to describe the interaction of a valence electron with the alkali core, which incorporates the correct asymptotic behavior in terms of dipolar polarizabilities, and the short-range exchange effects in terms of a hard core adjusted to give the correct energy for the valence electron. Based on this potential, simple wave functions are developed to describe the (H-alkali)+ and (alkali-alkali)+ ions. These wave functions exhibit some important structures of the ions, and provide a universal description of the properties of all (H-alkali)+ and (alkali-alkali)+ ions, in particular, the equilibrium separations of the nuclei and the corresponding dissociation energies. They also allow us to calculate the dipolar polarizabilities of Li2+, Na2+, K2+, Rb2+, and Cs2+.

  12. Multiple-Wavelength Metal/Halide Laser

    NASA Technical Reports Server (NTRS)

    Nerheim, N. M.

    1984-01-01

    Single device produces multiple lasing lines. Laser capable of producing many lasing lines has several reservoirs of halide lasant mixed with chlorides of copper, manganese and iron. Convection-control technique possible to rapidly change from one metal halide to another at maximum energy.

  13. Alkali-vapor lasers

    NASA Astrophysics Data System (ADS)

    Zweiback, J.; Komashko, A.; Krupke, W. F.

    2010-02-01

    We report on the results from several of our alkali laser systems. We show highly efficient performance from an alexandrite-pumped rubidium laser. Using a laser diode stack as a pump source, we demonstrate up to 145 W of average power from a CW system. We present a design for a transversely pumped demonstration system that will show all of the required laser physics for a high power system.

  14. The effects of dissolved halide anions on hydrogen bonding in liquid water.

    PubMed

    Smith, Jared D; Saykally, Richard J; Geissler, Phillip L

    2007-11-14

    It is widely believed that the addition of salts to water engenders structural changes in the hydrogen-bond network well beyond the adjacent shell of solvating molecules. Classification of many ions as "structure makers" and "structure breakers" has been based in part on corresponding changes in the vibrational spectra (Raman and IR). Here we show that changes in O-H vibrational spectra induced by the alkali halides in liquid water result instead from the actions of ions' electric fields on adjacent water molecules. Computer simulations that accurately reproduce our experimental measurements suggest that the statistics of hydrogen-bond strengths are only weakly modified beyond this first solvation shell. PMID:17958418

  15. Hygroscopicity Evaluation of Halide Scintillators

    SciTech Connect

    Zhuravleva, M; Stand, L; Wei, H; Hobbs, C. L.; Boatner, Lynn A; Ramey, Joanne Oxendine; Burger, Arnold; Rowe, E; Bhattacharya, P.; Tupitsyn, E; Melcher, Charles L

    2014-01-01

    A collaborative study of relative hygroscopicity of anhydrous halide scintillators grown at various laboratories is presented. We have developed a technique to evaluate moisture sensitivity of both raw materials and grown crystals, in which the moisture absorption rate is measured using a gravimetric analysis. Degradation of the scintillation performance was investigated by recording gamma-ray spectra and monitoring the photopeak position, count rate and energy resolution. The accompanying physical degradation of the samples exposed to ambient atmosphere was photographically recorded as well. The results were compared with ben

  16. Impurity segregation in zone-refined precursors for crystalline halide scintillators

    NASA Astrophysics Data System (ADS)

    Swider, S.; Lam, S.; Motakef, S.; Donohoe, E.; Coers, L.; Taylor, S.; Spencer, S.

    2015-06-01

    Successful growth of halide scintillator crystals depends on a supply of ultra-high purity (UHP) precursor materials. Metallic interstitials and substitutions may provide traps that quench luminescence. Oxygen impurities can create competing compounds within a matrix, such as oxyhalides, that disrupt crystallinity and nucleate cracks. Using mass spectroscopy and oxygen combustion analysis, we analyzed impurities in SrI2, EuI2, and YCl3 precursors before and after zone refining. The data show most alkali and alkali earth impurities segregated easily. However, with the exception of iron, many transition metals were incorporated into the solid. Reliable oxygen measurements proved difficult to achieve. Additional oxygen was measured in nitrates and sulfates, via ion chromatography. Zone refining reduced the overall impurity content, but levels remained above a 10 ppm target.

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  18. Rapid solid-state metathesis route to transition-metal doped titanias

    NASA Astrophysics Data System (ADS)

    Coleman, Nathaniel; Perera, Sujith; Gillan, Edward G.

    2015-12-01

    Rapid solid-state metathesis (SSM) reactions are often short-lived highly exothermic reactions that yield a molten alkali halide salt that aids in product growth and crystallization. SSM reactions may also produce kinetically stabilized structures due to the short (seconds) reaction times. This report describes the investigation of rapid SSM reactions in the synthesis of transition-metal doped titanias (M-TiO2). The dopant targeted compositions were ten mol percent and based on elemental analysis, many of the M-TiO2 samples were close to this targeted level. Based on surface analysis, some samples showed large enrichment in surface dopant content, particularly chromium and manganese doped samples. Due to the highly exothermic nature of these reactions, rutile structured TiO2 was observed in all cases. The M-TiO2 samples are visible colored and show magnetic and optical properties consistent with the dopant in an oxide environment. UV and visible photocatalytic experiments with these visibly colored rutile M-TiO2 powders showed that many of them are strongly absorbent for methylene blue dye and degrade the dye under both UV and visible light illumination. This work may open up SSM reactions as an alternate non-thermodynamic reaction strategy for dopant incorporation into a wide range of oxide and non-oxides.

  19. Shallow halogen vacancies in halide optoelectronic materials

    DOE PAGESBeta

    Shi, Hongliang; Du, Mao -Hua

    2014-11-05

    Halogen vacancies (VH) are usually deep color centers (F centers) in halides and can act as major electron traps or recombination centers. The deep VH contributes to the typically poor carrier transport properties in halides. However, several halides have recently emerged as excellent optoelectronic materials, e.g., CH3NH3PbI3 and TlBr. Both CH3NH3PbI3 and TlBr have been found to have shallow VH, in contrast to commonly seen deep VH in halides. In this paper, several halide optoelectronic materials, i.e., CH3NH3PbI3, CH3NH3SnI3 (photovoltaic materials), TlBr, and CsPbBr3, (gamma-ray detection materials) are studied to understand the material chemistry and structure that determine whether VHmore » is a shallow or deep defect in a halide material. It is found that crystal structure and chemistry of ns2 ions both play important roles in creating shallow VH in halides such as CH3NH3PbI3, CH3NH3SnI3, and TlBr. The key to identifying halides with shallow VH is to find the right crystal structures and compounds that suppress cation orbital hybridization at VH, such as those with long cation-cation distances and low anion coordination numbers, and those with crystal symmetry that prevents strong hybridization of cation dangling bond orbitals at VH. Furthermore, the results of this paper provide insight and guidance to identifying halides with shallow VH as good electronic and optoelectronic materials.« less

  20. Shallow halogen vacancies in halide optoelectronic materials

    NASA Astrophysics Data System (ADS)

    Shi, Hongliang; Du, Mao-Hua

    2014-11-01

    Halogen vacancies (VH ) are usually deep color centers (F centers) in halides and can act as major electron traps or recombination centers. The deep VH contributes to the typically poor carrier transport properties in halides. However, several halides have recently emerged as excellent optoelectronic materials, e.g., C H3N H3Pb I3 and TlBr. Both C H3N H3Pb I3 and TlBr have been found to have shallow VH , in contrast to commonly seen deep VH in halides. In this paper, several halide optoelectronic materials, i.e., C H3N H3Pb I3 , C H3N H3Sn I3 (photovoltaic materials), TlBr, and CsPbB r3 (gamma-ray detection materials) are studied to understand the material chemistry and structure that determine whether VH is a shallow or deep defect in a halide material. It is found that crystal structure and chemistry of n s2 ions both play important roles in creating shallow VH in halides such as C H3N H3Pb I3 , C H3N H3Sn I3 , and TlBr. The key to identifying halides with shallow VH is to find the right crystal structures and compounds that suppress cation orbital hybridization at VH , such as those with large cation-cation distances and low anion coordination numbers and those with crystal symmetry that prevents strong hybridization of cation dangling bond orbitals at VH . The results of this paper provide insight and guidance to identifying halides with shallow VH as good electronic and optoelectronic materials.

  1. Cross-Electrophile Coupling of Vinyl Halides with Alkyl Halides.

    PubMed

    Johnson, Keywan A; Biswas, Soumik; Weix, Daniel J

    2016-05-23

    An improved method for the reductive coupling of aryl and vinyl bromides with alkyl halides that gave high yields for a variety of substrates at room temperature with a low (2.5 to 0.5 mol %) catalyst loading is presented. Under the optimized conditions, difficult substrates, such as unhindered alkenyl bromides, can be coupled to give the desired olefins with minimal diene formation and good stereoretention. These improved conditions also worked well for aryl bromides. For example, a gram-scale reaction was demonstrated with 0.5 mol % catalyst loading, whereas reactions at 10 mol % catalyst loading completed in as little as 20 minutes. Finally, a low-cost single-component pre-catalyst, (bpy)NiI2 (bpy=2,2'-bipyridine) that is both air- and moisture-stable over a period of months was introduced. PMID:27017436

  2. PROCESS OF RECOVERING ALKALI METALS

    DOEpatents

    Wolkoff, J.

    1961-08-15

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

  3. Preparation of alkali metal dispersions

    NASA Technical Reports Server (NTRS)

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

    1968-01-01

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

  4. Purification of alkali metal nitrates

    DOEpatents

    Fiorucci, Louis C.; Gregory, Kevin M.

    1985-05-14

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

  5. Toxicity of organometal halide perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Babayigit, Aslihan; Ethirajan, Anitha; Muller, Marc; Conings, Bert

    2016-03-01

    In the last few years, the advent of metal halide perovskite solar cells has revolutionized the prospects of next-generation photovoltaics. As this technology is maturing at an exceptional rate, research on its environmental impact is becoming increasingly relevant.

  6. Hydrogen Halides on Jupiter and Saturn

    NASA Astrophysics Data System (ADS)

    Showman, Adam P.

    2001-07-01

    The quest to detect gaseous HCl, HBr, and HF in the atmospheres of Jupiter and Saturn has led to a tentative detection of 1 ppb HCl near Saturn's cloud deck. The detection is puzzling because, while these hydrogen halides may be present several scale heights below the clouds, they are expected to react with ammonia to form solid ammonium halide salts in the upper troposphere. I show that the loss timescale for condensation of gaseous hydrogen halides onto particles is ˜10 3-10 5 s for realistic cloud densities and particle sizes, which is much less than the ˜10 8 s residence time of upper tropospheric air. The hydrogen halides can only survive transport up to the cloud layer if less than 1 in 10 6 of their collisions with particle surfaces leads to condensation, which is unlikely. Even in the absence of foreign particles, homogeneous nucleation would probably prevent supersaturations in excess of a few hundred, which is ˜10 20-10 40 times too low to explain the observation. These calculations therefore suggest that hydrogen halides cannot exist at part-per-billion levels in the upper troposphere. The interplanetary source of halogens is also too low to produce detectable quantities of hydrogen halides except perhaps at pressures less than 1 mbar. A possible detection of chlorine by the Galileo probe at pressures exceeding 9 bars on Jupiter may be consistent with the equilibrium abundance of gaseous HCl or NH 4Cl.

  7. Rapid sonosynthesis of N-doped nano TiO2 on wool fabric at low temperature: introducing self-cleaning, hydrophilicity, antibacterial/antifungal properties with low alkali solubility, yellowness and cytotoxicity.

    PubMed

    Behzadnia, Amir; Montazer, Majid; Rashidi, Abousaeid; Mahmoudi Rad, Mahnaz

    2014-01-01

    Nano nitrogen-doped titanium dioxide was rapidly prepared by hydrolysis of titanium isopropoxide at 75-80°C using in situ sonochemical synthesis by introducing ammonia. Various concentrations of titanium isopropoxide were examined to deposit nano nitrogen-doped titanium dioxide through impregnation of the wool fabric in ultrasound bath followed by curing. The antibacterial/antifungal activities of wool samples were assessed against two common pathogenic bacteria including Escherichia coli and Staphylococcus aureus and the diploid fungus Candida albicans. The sonotreated wool fabrics indicated no adverse effects on human dermal fibroblasts. The presence of nanoparticles on the sonotreated wool fabrics were confirmed by FE-SEM images and EDS patterns and X-ray mapping and the crystalline size of nanoparticles were estimated through XRD results. The role of both pH and precursor concentration on the various properties of the fabric was investigated and the optimized conditions introduced using response surface methodology. PMID:25065604

  8. Dimming of metal halide lamps

    NASA Technical Reports Server (NTRS)

    Schurer, Kees

    1994-01-01

    We ran some tests on the effect of dimming of metal halide (MH) lamps upon the stability and the spectral quality of the light output. Lamps used were a new Philips lamp HPI-T 250W, a similar Philips lamp with a few thousand burning hours and a new Osram lamp HQI-T 250W/D. The ballast was a BBC type DJ 250/2KS, the starter a BAS TORGI type MZN 250 SE and the dimmer an Elstrom Control System type ERHQ-T 250. Power was derived from a Philips stabilizer, type PE 1602. Lamp output was monitored with a PAR meter. Spectra were taken at 100% and at 50% output as measured with the PAR meter. Lamps were allowed to stabilize at any setting for 30 minutes before measurements were made. Lamp manufacturers advise against dimming for fear of poor stability and intolerable changes of the spectrum. However, none of the lamps showed a decrease in stability, no flicker or wandering of the discharge, and the changes of the spectrum were not negligible, but certainly not dramatic. Lamps of either manufacture retain their white color, relative peak heights of spectral lines did shift, but no gaps in the spectrum occurred. Spectra taken at 50% with 30 minutes intervals coincided. Differences between the new and the older Philips lamp were noticeable, but not really significant.

  9. Upgrading platform using alkali metals

    SciTech Connect

    Gordon, John Howard

    2014-09-09

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

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

    NASA Astrophysics Data System (ADS)

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

    1983-07-01

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

  11. Diffusion of alkali species in porous tungsten substrates used in contact ionization sources

    SciTech Connect

    Chacon-Golcher, E.; Kwan, J.; Morse, E. C.

    2002-01-01

    Contact ionization (doped) sources used in current Heavy Ion Fusion experiments consist of a porous tungsten substrate doped with an alkali carbonate. In the early stages of the heating cycle (T - 600 C), the carbonate breaks down and releases the alkali atoms that then diffuse through the substrate. At the emitter surface there is a balance between the fast desorption rate of the alkali atoms (mostly as neutrals) and the slower replenishment rate from the substrate by diffusion. Time-resolved measurements of neutral particle evaporation rates at the emitter surface have been used to estimate the effective diffusion coefficient (D) that characterizes the migration of alkali species in the substrate. These estimates are consistent with the observed source lifetimes (tens of hrs.) and establish the alkali migration in the bulk as a diffusion-limited process. The measurements suggest that the faster migration rates (D {approx} 10{sup -5} - 10{sup -6} cm2/s) occur early during the heating cycle when the dominant species are the neutral alkali atoms. At operating temperatures there is a slower migration rate (D x 10-7cm2/sd) ue to the dominance of ions, which difise by a slower surface diffusion process.

  12. The Remarkable Reactivity of Aryl Halides with Nucleophiles

    ERIC Educational Resources Information Center

    Bunnett, Joseph F.

    1974-01-01

    Discusses the reactivity of aryl halides with nucleophilic or basic reagents, including nucleophilic attacks on carbon, hydrogen, halogen, and arynes. Suggestions are made concerning revisions of the sections on aryl halide chemistry courses and the corresponding chapters in textbooks. (CC)

  13. Shallow halogen vacancies in halide optoelectronic materials

    SciTech Connect

    Shi, Hongliang; Du, Mao -Hua

    2014-11-05

    Halogen vacancies (VH) are usually deep color centers (F centers) in halides and can act as major electron traps or recombination centers. The deep VH contributes to the typically poor carrier transport properties in halides. However, several halides have recently emerged as excellent optoelectronic materials, e.g., CH3NH3PbI3 and TlBr. Both CH3NH3PbI3 and TlBr have been found to have shallow VH, in contrast to commonly seen deep VH in halides. In this paper, several halide optoelectronic materials, i.e., CH3NH3PbI3, CH3NH3SnI3 (photovoltaic materials), TlBr, and CsPbBr3, (gamma-ray detection materials) are studied to understand the material chemistry and structure that determine whether VH is a shallow or deep defect in a halide material. It is found that crystal structure and chemistry of ns2 ions both play important roles in creating shallow VH in halides such as CH3NH3PbI3, CH3NH3SnI3, and TlBr. The key to identifying halides with shallow VH is to find the right crystal structures and compounds that suppress cation orbital hybridization at VH, such as those with long cation-cation distances and low anion coordination numbers, and those with crystal symmetry that prevents strong hybridization of cation dangling bond orbitals at VH. Furthermore, the results of this paper provide insight and guidance to identifying halides with shallow VH as good electronic and optoelectronic materials.

  14. Effects of isoelectronic and halide surfactants on compound semiconductors

    NASA Astrophysics Data System (ADS)

    Howard, Alexander David

    Isoelectronic surfactants Sb, Bi, and N, have proven to increase the doping efficiency of Zn while concurrently reducing the unintentional impurities C, Si, and S in GaP. Additionally, surfactant Sb and N have demonstrated that altering the incorporation efficiency in GaP is also possible with a surfactant surface coverage of less than one. Halide surfactants Br and Cl were shown to systematically destroy ordering in GaInP. Furthermore, a distinct correlation between increasing surfactant Br or Cl in the vapor and surface roughness was evident. This work is presented in three main sections. First, surfactants Sb and Bi, from the pyrolysis of TMSb and TMBi, were examined to determine the effect on Zn doping in GaP. The data demonstrate that the incorporation of Zn can be increased by an order of magnitude in GaP to a value of approximately 1020 cm-3, the highest value reported to date. Additionally, these same surfactants lead to significant decreases in carbon contamination during growth. At high growth temperatures, the reduction can be as large as 100 x in GaP. Second, the role of steps versus the singular surface between steps was studied by using a surfactant fractional surface coverage of less than one. When surfactant Sb was used, the Zn concentration was increased and C was reduced. However, there was no discernable change in incorporation efficiency over the entire range of surfactant Sb studied. Interestingly, surfactant N showed a linear increase in the Zn doping the with amount of surfactant present during growth resulting in an increase of 2 x at the highest flow rate used. Third, halide surfactants Br and Cl, carbon-tetrabromide and carbon-tetrachloride, were studied for their effects on ordering in GaInP. Bromine systematically decreased the amount of CuPt ordering observed by photoluminescence and transmission electron microscopy. Both surfactants Br and Cl were shown to significantly increase the surface roughness, which is postulated to be the

  15. 40 CFR 721.575 - Substituted alkyl halide.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted alkyl halide. 721.575... Substances § 721.575 Substituted alkyl halide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as substituted alkyl halide (PMN P-83-1222)...

  16. Method for recovering hydrocarbons from molten metal halides

    DOEpatents

    Pell, Melvyn B.

    1979-01-01

    In a process for hydrocracking heavy carbonaceous materials by contacting such carbonaceous materials with hydrogen in the presence of a molten metal halide catalyst to produce hydrocarbons having lower molecular weights and thereafter recovering the hydrocarbons so produced from the molten metal halide, an improvement comprising injecting into the spent molten metal halide, a liquid low-boiling hydrocarbon stream is disclosed.

  17. Alkali slurry ozonation to produce a high capacity nickel battery material

    DOEpatents

    Jackovitz, John F.; Pantier, Earl A.

    1984-11-06

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

  18. Recent advances in technetium halide chemistry.

    PubMed

    Poineau, Frederic; Johnstone, Erik V; Czerwinski, Kenneth R; Sattelberger, Alfred P

    2014-02-18

    Transition metal binary halides are fundamental compounds, and the study of their structure, bonding, and other properties gives chemists a better understanding of physicochemical trends across the periodic table. One transition metal whose halide chemistry is underdeveloped is technetium, the lightest radioelement. For half a century, the halide chemistry of technetium has been defined by three compounds: TcF6, TcF5, and TcCl4. The absence of Tc binary bromides and iodides in the literature was surprising considering the existence of such compounds for all of the elements surrounding technetium. The common synthetic routes that scientists use to obtain binary halides of the neighboring elements, such as sealed tube reactions between elements and flowing gas reactions between a molecular complex and HX gas (X = Cl, Br, or I), had not been reported for technetium. In this Account, we discuss how we used these routes to revisit the halide chemistry of technetium. We report seven new phases: TcBr4, TcBr3, α/β-TcCl3, α/β-TcCl2, and TcI3. Technetium tetrachloride and tetrabromide are isostructural to PtX4 (X = Cl or Br) and consist of infinite chains of edge-sharing TcX6 octahedra. Trivalent technetium halides are isostructural to ruthenium and molybdenum (β-TcCl3, TcBr3, and TcI3) and to rhenium (α-TcCl3). Technetium tribromide and triiodide exhibit the TiI3 structure-type and consist of infinite chains of face-sharing TcX6 (X = Br or I) octahedra. Concerning the trichlorides, β-TcCl3 crystallizes with the AlCl3 structure-type and consists of infinite layers of edge-sharing TcCl6 octahedra, while α-TcCl3 consists of infinite layers of Tc3Cl9 units. Both phases of technetium dichloride exhibit new structure-types that consist of infinite chains of [Tc2Cl8] units. For the technetium binary halides, we studied the metal-metal interaction by theoretical methods and magnetic measurements. The change of the electronic configuration of the metal atom from d(3) (Tc

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  20. The electronic structure of alkali aurides. A four-component Dirac-Kohn-Sham study.

    PubMed

    Belpassi, Leonardo; Tarantelli, Francesco; Sgamellotti, Antonio; Quiney, Harry M

    2006-04-01

    Spectroscopic constants, including dissociation energies, harmonic and anharmonic vibrational frequencies, and dipole moments, are calculated for the complete alkali auride series (LiAu, NaAu, KAu, RbAu, CsAu). The four-component formulation of relativistic density functional theory has been employed in this study, using the G-spinor basis sets implemented recently in the program BERTHA. The performance of four standard nonrelativistic density functionals employed is investigated by comparing the results with the best available theoretical and experimental data. The present work provides the first theoretical predictions on the molecular properties of RbAu. The intermetallic bond that occurs in the alkali auride series is highly polar and is characterized by a large charge transfer from the alkali metals to gold. The extent of this electron transfer has been investigated using several different charge analysis methods, enabling us to reach some general conclusions on their relative performance. We further report a detailed analysis of the topological properties of relativistic electron density in the bonding region, discussing the features of this approach which characterize the nature of the chemical bond. We have also computed the fully relativistic density for the alkali halides MBr and MI (M = Li, Na, K, Rb, and Cs). The comparative study shows that, on the basis of several topological properties and the variation in bond lengths, the gold atom behaves similarly to a halogen intermediate between Br and I. PMID:16571062

  1. Hydrothermal alkali metal catalyst recovery process

    DOEpatents

    Eakman, James M.; Clavenna, LeRoy R.

    1979-01-01

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

  2. Alkali Halide Opacity in Brown Dwarf and Cool Stellar Atmospheres: A Study of Lithium Chloride

    NASA Astrophysics Data System (ADS)

    Kirby, K.; Weck, P. F.; Schweitzer, A.; Stancil, P. C.; Hauschildt, P. H.

    2003-12-01

    Recent thermochemical equilibrium calculations have revealed the important role played by lithium chloride in the lithium chemistry of cool dwarf atmospheres (K. Lodders 1999, ApJ 519, 793). Indeed, LiCl appears to be the dominant Li-bearing gas over an extended domain of the (P,T) diagram, typically for temperatures below 1500 K. LiCl has a large dipole moment in its ground electronic state which can give rise to intense rovibrational line spectra. In addition, LiCl can make dipole transitions to several low-lying unbound excited states, causing dissociation of the molecule. For these reasons, LiCl may be a significant source of line and continuum opacity in brown dwarf and cool stellar atmospheres. In this work, we report calculations of complete lists of line oscillator strengths and photodissociation cross sections for the low-lying electronic states of LiCl. We have performed single- and double-excitation configuration interaction calculations using the ALCHEMY ab initio package (Mc Lean et al. 1991, MOTECC 91, Elsevier, Leiden) and obtained the potential curves and the corresponding dipole transition moment functions between the X 1Σ ^+ ground state and the B 1Σ ^+ and A 1Π excited states. The resulting line oscillator strengths and molecular photodissociation cross sections have been included in the PHOENIX stellar atmosphere code (Hauschildt & Baron 1999, J. Comput. App. Math. 102, 41). 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 (EOS). This work was supported in part by NSF grants AST-9720704 and AST-0086246, NASA grants NAG5-8425, NAG5-9222, and NAG5-10551 as well as NASA/JPL grant 961582.

  3. Elastic properties of alpha quartz and the alkali halides based on an interatomic force model.

    NASA Technical Reports Server (NTRS)

    Weidner, D. J.; Simmons, G.

    1972-01-01

    A two-body central-force atomic model can be used to describe accurately the elastic properties of alpha quartz if the nontetrahedral O:O forces are included. The strength of the Si:O interaction has little effect on the bulk modulus. The technique is sufficiently general to allow calculations of the elastic properties of a specified structure under arbitrary pressure from a complete description of the interatomic forces. The elastic constants for the NaCl structure and the CsCl structure are examined. Our model includes two-body, central, anion-anion, anion-cation, and electrostatic interactions.

  4. The aluminum electrode in AlCl3-alkali-halide melts

    NASA Technical Reports Server (NTRS)

    Holleck, G. L.; Giner, J.

    1972-01-01

    Passivation phenomena were observed upon cathodic and anodic polarization of the Al electrode in AlCl3-KCl-NaCl melts between 100 and 160 C. They are caused by formation of a solid salt layer at the electrode surface resulting from concentration changes upon current flow. The anodic limiting currents increased with temperature and with decreasing AlCl3 content of the melt. Current voltage curves obtained on a rotating aluminum disk showed a linear relationship between the anodic limiting current and 1/sq root of 2 pi (rps). Upon cathodic polarization dentrite formation occurs at the Al electrode. The activation overvoltage in AlCl3-KCl-NaCl (57.5-12.5-20 mol%) was determined by galvanostatic current step methods. An apparent exchange current density of 270 mA/cm2 at 130 C and a double layer capacity of 40 plus or minus 10 microfarad/cm2 were measured.

  5. The aluminum electrode in AlCl3-alkali-halide melts.

    NASA Technical Reports Server (NTRS)

    Holleck, G. L.; Giner, J.

    1972-01-01

    Passivation phenomena have been observed upon cathodic and anodic polarization of the Al electrode in AlCl3-KCl-NaCl melts between 100 and 160 C. They are caused by formation of a solid salt layer at the electrode surface resulting from concentration changes upon current flow. The anodic limiting currents increased with temperature and with decreasing AlCl3 content of the melt. Current voltage curves obtained on a rotating aluminum disk showed a linear relationship between the anodic limiting current and omega to the minus 1/2 power. Upon cathodic polarization, dendrite formation occurs at the Al electrode. The activation overvoltage in AlCl3-KCl-NaCl was determined by galvanostatic current step methods. An apparent exchange current density of 270 mA/sq cm at 130 C and a double layer capacity of 40 plus or minus 10 microfarad/sq cm were measured.

  6. Extreme ultraviolet quantum efficiency of opaque alkali halide photocathodes on microchannel plates

    NASA Technical Reports Server (NTRS)

    Siegmund, O. H. W.; Everman, E.; Vallerga, J. V.; Lampton, M.

    1988-01-01

    Comprehensive measurements are presented for the quantum detection efficiency (QDE) of the microchannel plate materials CsI, KBr, KCl, and MgF2, over the 44-1800 A wavelength range. QDEs in excess of 40 percent are achieved by several materials in specific wavelength regions of the EUV. Structure is noted in the wavelength dependence of the QDE that is directly related to the valence-band/conduction-band gap energy and the onset of atomic-like resonant transitions. A simple photocathode model allows interpretation of these features, together with the QDE efficiency variation, as a function of illumination angle.

  7. Is surface layering of aqueous alkali halides determined by ion pairing in the bulk solution?

    NASA Astrophysics Data System (ADS)

    Brandes, Eva; Stage, Christiane; Motschmann, Hubert; Rieder, Julian; Buchner, Richard

    2014-11-01

    This contribution aims to elucidate the connection between ion-ion-solvent interactions in the bulk of aqueous electrolyte solutions and the properties of their liquid-air interface. In particular, we were interested in the conditions under which ion pairs form at the surface and whether this is linked to ion pairing in the bulk. For this reason different combinations of hard (Cl-, Li+) and soft ions (I-, Cs+) were investigated. Ion hydration and possible ion association in the bulk was probed with dielectric relaxation spectroscopy. This technique monitors the cooperative reorientation of the dipolar solvent molecules and detects all ion-pair species possibly present in the solution. At the interface, the formation of contact ion pairs was investigated by infrared-visible-sum frequency spectroscopy (SFG). This nonlinear optical technique possesses an inherent surface specificity and can be used for the characterization of interfacial water. The intensity of the SFG-active vibrational stretching modes depends on the number of oriented water molecules. The electric field at the surface of a charged aqueous interface aligns the water dipoles, which in turn increases the SFG response. Hence, the enhancement of the oscillator strengths of the water vibrational modes can be used to draw some conclusions on the strengths and geometrical extension of the electric field. The formation of ion pairs at the interface reduces the intensity of the band associated with hydrogen-bonded water. The underlying theory is presented. The combined data show that there are no contact ion pairs in the bulk of the fluid and—at best—only small amounts of solvent shared ion pairs. On the other hand, the combination of hard/hard or soft/soft ions leads to the formation of ion pairs at the liquid-air interface.

  8. Properties of alkali-halide salt solutions about polarizable nanoparticle solutes for different ion models

    NASA Astrophysics Data System (ADS)

    Wynveen, Aaron; Bresme, Fernando

    2010-10-01

    We investigate the distributions of various salts about large hydrophobic polarizable solutes in aqueous electrolyte solutions. The solutes are modeled as nanometer-sized cylindrical objects, a scale relevant to biomolecules and nanomaterials, and particularly high aspect ratio nanoparticles. Interactions, including image charge forces arising from the finite polarizability of the solute, between explicit solvent/ions and the solute are computed explicitly using a molecular dynamics simulation methodology we have recently introduced. Comparisons are made between several salt species and different models of the force fields for each ionic component of the salt. We find evidence that both small cations, Li+, and large anions, I-, adsorb at hydrophobic interfaces. Our results indicate that the ion structure about the solute is strongly dependent on the force field investigated, suggesting that ion selectivity is quite sensitive to the respective parameters defining the ion's size and binding energy as well as to the polarizability of the solute.

  9. Dipole-driven self-organization of zwitterionic molecules on alkali halide surfaces.

    PubMed

    Nony, Laurent; Bocquet, Franck; Para, Franck; Chérioux, Frédéric; Duverger, Eric; Palmino, Frank; Luzet, Vincent; Loppacher, Christian

    2012-01-01

    We investigated the adsorption of 4-methoxy-4'-(3-sulfonatopropyl)stilbazolium (MSPS) on different ionic (001) crystal surfaces by means of noncontact atomic force microscopy. MSPS is a zwitterionic molecule with a strong electric dipole moment. When deposited onto the substrates at room temperature, MSPS diffuses to step edges and defect sites and forms disordered assemblies of molecules. Subsequent annealing induces two different processes: First, at high coverage, the molecules assemble into a well-organized quadratic lattice, which is perfectly aligned with the <110> directions of the substrate surface (i.e., rows of equal charges) and which produces a Moiré pattern due to coincidences with the substrate lattice constant. Second, at low coverage, we observe step edges decorated with MSPS molecules that run along the <110> direction. These polar steps most probably minimize the surface energy as they counterbalance the molecular dipole by presenting oppositely charged ions on the rearranged step edge. PMID:22497002

  10. Dipole-driven self-organization of zwitterionic molecules on alkali halide surfaces

    PubMed Central

    Nony, Laurent; Bocquet, Franck; Para, Franck; Chérioux, Frédéric; Duverger, Eric; Palmino, Frank; Luzet, Vincent

    2012-01-01

    Summary We investigated the adsorption of 4-methoxy-4′-(3-sulfonatopropyl)stilbazolium (MSPS) on different ionic (001) crystal surfaces by means of noncontact atomic force microscopy. MSPS is a zwitterionic molecule with a strong electric dipole moment. When deposited onto the substrates at room temperature, MSPS diffuses to step edges and defect sites and forms disordered assemblies of molecules. Subsequent annealing induces two different processes: First, at high coverage, the molecules assemble into a well-organized quadratic lattice, which is perfectly aligned with the <110> directions of the substrate surface (i.e., rows of equal charges) and which produces a Moiré pattern due to coincidences with the substrate lattice constant. Second, at low coverage, we observe step edges decorated with MSPS molecules that run along the <110> direction. These polar steps most probably minimize the surface energy as they counterbalance the molecular dipole by presenting oppositely charged ions on the rearranged step edge. PMID:22497002

  11. Electronic line-up in light-emitting diodes with alkali-halide/metal cathodes

    NASA Astrophysics Data System (ADS)

    Brown, T. M.; Friend, R. H.; Millard, I. S.; Lacey, D. J.; Butler, T.; Burroughes, J. H.; Cacialli, F.

    2003-05-01

    The electronic nature of metal-semiconductor contacts is a fundamental issue in the understanding of semiconductor device physics, because such contacts control charge injection, and therefore play a major role in determining the electron/hole population in the semiconductor itself. This role is particularly important for organic semiconductors as they are generally used in their pristine, undoped form. Here, we review our progress in the understanding of the energy level line-up in finished, blue-emitting, polyfluorene-based light-emitting diodes, which exploit LiF and CsF thin films in combination with Ca and Al to obtain cathodes with low injection barriers. We have used electroabsorption measurements, as they allow the noninvasive determination of the built-in potential when changing the cathode. This provides precious experimental information on the alteration of the polymer/cathode interfacial energy level line-up. The latter is found to depend strongly on the electrode work function. Thus, the Schottky-Mott model for the energy level alignment is found to be a better first-order approximation than those models where strong pinning or large interface dipoles determine the alignment (e.g., Bardeen model), except for electrodes that extensively react with the polymer, and introduce deep gap states. In addition, we show results that validate the approximation of rigid tilting of polymer energy levels with bias (for biases for which no significant injection of carriers occurs). To investigate further the consequences of the electronic line-up on device operation, we complemented the electroabsorption measurements with characterization of the emissive and transport properties of the light-emitting diodes, and confirmed that the cathodic barrier lowering in CsF/Ca/Al and LiF/Ca/Al electrodes leads to the best improvements in electron injection. We found that luminance and overall current are greatly affected by the barrier-reducing cathodes, indicating a truly bipolar transport, with comparable electron and hole currents. We also found significant indications of CsF/Ca/Al cathodes strongly reacting with the polymer, which is suggestive of CsF dissociation and diffusion in the bulk of the polymer.

  12. Vibration-Resistant Support for Halide Lamps

    NASA Technical Reports Server (NTRS)

    Kiss, J.

    1987-01-01

    Lamp envelope protected against breakage. Old and new mounts for halide arc lamp sealed in housing with parabolic refector and quartz window. New version supports lamp with compliant garters instead of rigid brazed joint at top and dimensionally unstable finger stock at bottom.

  13. Photoluminescence and anti-deliquesce of cesium iodide and its sodium-doped films deposited by thermal evaporation at high deposition rates

    NASA Astrophysics Data System (ADS)

    Hsu, Jin-Cherng; Chiang, Yueh-Sheng; Ma, Yu-Sheng

    2013-03-01

    Cesium iodide (CsI) and sodium iodide (NaI) are good scintillators due to their high luminescence efficiency. These alkali halides can be excited by ultra-violet or by ionizing radiation. In this study, CsI and its Na-doped films about 8 μm thick were deposited by thermal evaporation boat without heating substrates at high deposition rates of 30, 50, 70, 90, and 110 nm/sec, respectively. The as-deposited films were sequentially deposited a silicon dioxide film to protect from deliquesce. And, the films were also post-annealed in vacuum at 150, 200, 250, and 300 °C, respectively. We calculated the packing densities of the samples according to the measurements of Fourier transform infrared spectroscopy (FTIR) and observed the luminescence properties by photoluminescence (PL) system. The surfaces and cross sections of the films were investigated by scanning electron microscope (SEM). From the above measurements we can find the optimal deposition rate of 90 nm/sec and post-annealing temperature of 250 °C in vacuum for the asdeposited cesium iodide and its sodium-doped films.

  14. Electrolytic method to make alkali alcoholates using ion conducting alkali electrolyte/separator

    DOEpatents

    Joshi, Ashok V.; Balagopal, Shekar; Pendelton, Justin

    2011-12-13

    Alkali alcoholates, also called alkali alkoxides, are produced from alkali metal salt solutions and alcohol using a three-compartment electrolytic cell. The electrolytic cell includes an anolyte compartment configured with an anode, a buffer compartment, and a catholyte compartment configured with a cathode. An alkali ion conducting solid electrolyte configured to selectively transport alkali ions is positioned between the anolyte compartment and the buffer compartment. An alkali ion permeable separator is positioned between the buffer compartment and the catholyte compartment. The catholyte solution may include an alkali alcoholate and alcohol. The anolyte solution may include at least one alkali salt. The buffer compartment solution may include a soluble alkali salt and an alkali alcoholate in alcohol.

  15. The calcium-alkali syndrome.

    PubMed

    Arroyo, Mariangeli; Fenves, Andrew Z; Emmett, Michael

    2013-04-01

    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 by the ingestion of large amounts of calcium carbonate salts to prevent or treat osteoporosis and dyspepsia. We describe a 78-year-old woman who presented with weakness, malaise, and confusion. She was found to have hypercalcemia, acute renal failure, and metabolic alkalosis. Upon further questioning, she reported use of large amounts of calcium carbonate tablets to treat recent heartburn symptoms. Calcium supplements were discontinued, and she was treated with intravenous normal saline. After 5 days, the calcium and bicarbonate levels normalized and renal function returned to baseline. In this article, we review the pathogenesis of the calcium-alkali syndrome as well as the differences between the traditional and modern syndromes. PMID:23543983

  16. Theoretical characterization of dihydrogen adducts with halide anions

    NASA Astrophysics Data System (ADS)

    Vitillo, Jenny G.; Damin, Alessandro; Zecchina, Adriano; Ricchiardi, Gabriele

    2006-06-01

    The interaction between a hydrogen molecule and the halide anions F-, Cl-, Br-, and I- has been studied at different levels of theory and with different basis sets. The most stable configurations of the complexes have a linear geometry, while the t-shaped complexes are saddle points on the potential energy surface, opposite to what is observed for alkali cations. An electrostatic analysis conducted on the resulting adducts has highlighted the predominance of the electrostatic term in the complexation energy and, in particular, of the quadrupole- and dipole-polarizability dependent contributions. Another striking difference with respect to the positive ions, is the fact that although the binding energies have similar values (ranging between 25 and 3kJ/mol for F- and I-, respectively), the vibrational shift of the ν˜H-H and in general the perturbation of the hydrogen molecule in complexes are much greater in the complexes with anions (Δν˜H-H ranges between -720 and -65cm-1). Another difference with respect to the interaction with cations is a larger charge transfer from the anion to the hydrogen molecule. The Δν˜ is the result of the cooperative role of the electrostatics and of the charge transfer in the interaction. The correlation between binding energies and vibrational shift is far from linear, contrary to what is observed for cation complexes, in accordance with the higher polarizability and dynamic polarizability of the molecule along the molecular axis. The observed correlation may be valuable in the interpretation of spectra and thermodynamic properties of adsorbed H2 in storage materials.

  17. Double-Diffusive Convection During Growth of Halides and Selenides

    NASA Technical Reports Server (NTRS)

    Singh, N. B.; Su, Ching-Hua; Duval, Walter M. B.

    2015-01-01

    Heavy metal halides and selenides have unique properties which make them excellent materials for chemical, biological and radiological sensors. Recently it has been shown that selenohalides are even better materials than halides or selenides for gamma-ray detection. These materials also meet the strong needs of a wide band imaging technology to cover ultra-violet (UV), midwave infrared wavelength (MWIR) to very long wavelength infrared (VLWIR) region for hyperspectral imager components such as etalon filters and acousto-optic tunable filters (AO). In fact AOTF based imagers based on these materials have some superiority than imagers based on liquid crystals, FTIR, Fabry-Perot, grating, etalon, electro-optic modulation, piezoelectric and several other concepts. For example, broadband spectral and imagers have problems of processing large amount of information during real-time observation. Acousto-Optic Tunable Filter (AOTF) imagers are being developed to fill the need of reducing processing time of data, low cost operation and key to achieving the goal of covering long-wave infrared (LWIR). At the present time spectral imaging systems are based on the use of diffraction gratings are typically used in a pushbroom or whiskbroom mode. They are mostly used in systems and acquire large amounts of hyperspectral data that is processed off-line later. In contrast, acousto-optic tunable filter spectral imagers require very little image processing, providing new strategies for object recognition and tracking. They are ideally suited for tactical situations requiring immediate real-time image processing. But the performance of these imagers depends on the quality and homogeneity of acousto-optic materials. In addition for many systems requirements are so demanding that crystals up to sizes of 10 cm length are desired. We have studied several selenides and halide crystals for laser and AO imagers for MWIR and LWIR wavelength regions. We have grown and fabricated crystals of

  18. Transport of Soil Halides through Rice Paddies: A Viable Mechanism for Rapid Dispersion of the Soil Halide Reservoir

    NASA Astrophysics Data System (ADS)

    Redeker, K. R.; Manley, S.; Wang, N.; Cicerone, R.

    2002-05-01

    On short time scales (1-10 years) soil halide concentrations have been assumed to be primarily driven by leaching and deposition processes. Recent results however, have shown that terrestrial plants volatilize soil halides in the form of methyl halides. Emissions of methyl chloride, methyl bromide and methyl iodide represent major pathways for delivery of inorganic halogen radicals to the atmosphere. Inorganic halogen radicals destroy ozone in the stratosphere and modify the oxidative capacity of the lower atmosphere. We have previously shown that rice paddies emit methyl halides and that emissions depend on growth stage of the rice plant as well as field water management. We show here that rice grown in a greenhouse at UCI is capable of volatilizing and/or storing up to 30%, 5%, and 10% of the available chloride, bromide and iodide within the top meter of soil. The percent of plant tissue halide volatilized as methyl halide over the course of the season is calculated to be 0.05%, 0.25% and 85.0% for chloride, bromide and iodide. We compare our greenhouse soil halide concentrations to other commercial rice fields around the world and estimate the e-folding time for soil halides within each region. We suggest that rice agriculture is the driving removal mechanism for halides within rice paddies and that terrestrial plants play a larger role in global cycling of halides than previously estimated.

  19. Flame inhibition by hydrogen halides - Some spectroscopic measurements

    NASA Technical Reports Server (NTRS)

    Lerner, N. R.; Cagliostro, D. E.

    1973-01-01

    The far-ultraviolet absorption spectrum of an air-propane diffusion flame inhibited with hydrogen halides has been studied. Plots of the absorption of light by hydrogen halides as a function of position in the flame and also as a function of the amount of hydrogen halide added to the flame have been obtained. The hydrogen halides are shown to be more stable on the fuel side of the reaction zone than they are on the air side. Thermal diffusion is seen to be important in determining the concentration distribution of the heavier hydrogen halides in diffusion flames. The relationship between the concentration distribution of the hydrogen halides in the flame and the flame inhibition mechanism is discussed.

  20. Morphology-Controlled Synthesis of Organometal Halide Perovskite Inverse Opals.

    PubMed

    Chen, Kun; Tüysüz, Harun

    2015-11-01

    The booming development of organometal halide perovskites in recent years has prompted the exploration of morphology-control strategies to improve their performance in photovoltaic, photonic, and optoelectronic applications. However, the preparation of organometal halide perovskites with high hierarchical architecture is still highly challenging and a general morphology-control method for various organometal halide perovskites has not been achieved. A mild and scalable method to prepare organometal halide perovskites in inverse opal morphology is presented that uses a polystyrene-based artificial opal as hard template. Our method is flexible and compatible with different halides and organic ammonium compositions. Thus, the perovskite inverse opal maintains the advantage of straightforward structure and band gap engineering. Furthermore, optoelectronic investigations reveal that morphology exerted influence on the conducting nature of organometal halide perovskites. PMID:26376773

  1. The Oxidation State of Europium in Halide Glasses

    PubMed Central

    Weber, J.K.R.; Vu, M.; Paßlick, C.; Schweizer, S.; Brown, D.E.; Johnson, C.E.; Johnson, J.A.

    2012-01-01

    The luminescent properties of divalent europium ions can be exploited to produce storage phosphors for x-ray imaging applications. The relatively high cost and limited availability of divalent europium halides makes it desirable to synthesize them from the readily available trivalent salts. In this work, samples of pure EuCl3 and fluoride glass melts doped with EuCl3 were processed at 700-800 °C in an inert atmosphere furnace. The Eu oxidation state in the resulting materials was determined using fluorescence and Mössbauer spectroscopy. Heat treatment of pure EuCl3 for 10 minutes at 710 °C resulted in a material comprising approximately equal amounts of Eu2+ and Eu3+. Glasses made using mixtures of EuCl2 and EuCl3 in the starting material contained both oxidation states. This paper describes the sample preparation and analysis and discusses the results in the context of chemical equilibria in the melts. PMID:22101252

  2. Calcium Phosphate: A potential host for halide contaminated plutonium wastes.

    SciTech Connect

    Metcalfe, Brian L.; Donald, Ian W.; Fong, Shirley K.; Gerrard, Lee A.; Strachan, Denis M.; Scheele, Randall D.

    2009-07-06

    The presence of significant quantities of fluoride and chloride in four types of legacy wastes from plutonium pyrochemical reprocessing required the development of a new wasteform which could adequately immobilize the halides in addition to the Pu and Am. Using a simulant chloride-based waste (Type I waste) and Sm as the surrogate for the Pu3+ and Am3+ present in the waste, AWE developed a process which utilised Ca3(PO4)2 as the host material. The waste was successfully incorporated into two crystalline phases, chlorapatite, [Ca5(PO4)3Cl], and spodiosite, [Ca2(PO4)Cl]. Radioactive studies performed at PNNL with 239Pu and 241Am confirmed the process. A slightly modified version of the process in which CaHPO4 was used as the host was successful in immobilizing a more complex multi-cation oxide–based waste (Type II) which contained significant concentrations of Cl and F in addition to 239Pu and 241Am. This waste resulted in the formation of cation-doped whitlockite, Ca3-xMgx(PO4)2, β-calcium phosphate, β-Ca2P2O7 and chlor-fluorapatite rather than the chlorapatite and spodiosite formed with Type I waste.

  3. Interface Engineering in Metal Halides Perovskites: From molecules to devices

    NASA Astrophysics Data System (ADS)

    Petrozza, Annamaria

    In this talk we review our recent studies which aim to clarify the relationship between structural and electronic properties from a molecular to mesoscopic level. First we identify the markers for local disorder at molecular level by using Raman Spectroscopy as a probe. Then, we exploit such a tool to explore the role of microstructure on the absorption and emission properties of the semiconductor looking both at polycrystalline thin films and single crystals. We address the controversy surrounding electron - hole interactions and excitonic effects. We show that in hybrid lead-halide perovskites dielectric screening also depends on the local microstructure of the hybrid crystals and not only on its chemical composition. This leads to the possibility of band gap engineering and the consequent control of the elementary photo-excitation dynamics that determine the perovskites' performances in different optoelectronic devices. Finally, the role of interface engineering, the effect of ion migration, and interface doping on charge extraction will be elucidated to provide a guideline for the design of hysteresis free solar cells. 1)G. Grancini & AR Srimath Kandada et al., Nature Photonics, 9 (10), 695-701, 2015 2) C. Tao et al,'' Energy Environ. Sci.,8, 2365-2370, 2015

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

    SciTech Connect

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

    2014-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-09-01

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

  6. Lanthanide-halide based humidity indicators

    DOEpatents

    Beitz, James V.; Williams, Clayton W.

    2008-01-01

    The present invention discloses a lanthanide-halide based humidity indicator and method of producing such indicator. The color of the present invention indicates the humidity of an atmosphere to which it is exposed. For example, impregnating an adsorbent support such as silica gel with an aqueous solution of the europium-containing reagent solution described herein, and dehydrating the support to dryness forms a substance with a yellow color. When this substance is exposed to a humid atmosphere the water vapor from the air is adsorbed into the coating on the pore surface of the silica gel. As the water content of the coating increases, the visual color of the coated silica gel changes from yellow to white. The color change is due to the water combining with the lanthanide-halide complex on the pores of the gel.

  7. EVALUATION OF METHODS FOR THE DETERMINATION OF TOTAL ORGANIC HALIDE IN WATER AND WASTE

    EPA Science Inventory

    Various methods for the determination of total organic halides (TOX) in groundwater and in waste oil samples have been evaluated. Of three inorganic halide species generation approaches and three inorganic halide determinative techniques evaluated for groundwater analyses, one co...

  8. Progress in Understanding Alkali-Alkali Spin Relaxation

    NASA Astrophysics Data System (ADS)

    Erickson, Christopher J.; Happer, William; Chann, Bien; Kadlecek, Stephen; Anderson, L. W.; Walker, Thad G.

    2000-06-01

    In extensive experiments we have shown that a spin interaction with a relatively long correlation time causes much of the spin relaxation in very dense alkali-metal vapors. The spin relaxation is affected by the pressure of the helium or nitrogen buffer gas, although there is little dependence at pressures above one atmosphere. There are substantial differences in the relaxation rates for different isotopes of the same element, for example ^87Rb and ^85Rb. We have completed extensive modeling of how singlet and triplet dimers and doublet trimers of the alkali-metal atoms could cause spin relaxation in dense alkali-metal vapors. In the case of doublet trimers or triplet dimers, we assume the main coupling to the nuclear spins is through the Fermi Contact interaction with the unpaired electrons. Spin loss to the rotation of the molecule is assumed to occur through the electronic spin-rotation and spin-axis (dipole-dipole) interactions for the triplet dimers. For the singlet dimers, we assume that the nuclear spins couple directly to the rotational angular momentum of the molecule through the electric quadrupole interaction. We account for all of the total nuclear spin states that occur for the dimers and trimers. We have also considered the possibility that the collisional breakup and formation rates of the dimers or trimers could saturate with increasing buffer gas pressure. Such saturation occurs in many other unimolecular reactions and is often ascribed to breakup through activated states.

  9. Interpulse kinetics in copper and copper halide lasers

    NASA Technical Reports Server (NTRS)

    Harstad, K. G.

    1983-01-01

    The various rate processes that govern the interpulse relaxation in metal vapor and metal halide vapor lasers are considered. Computer calculations indicate that the rapid metastable levels relaxation observed in copper and copper halide laser experiments requires the existence of a relatively small resonance in the cross section for metastable excitation or deexcitation near threshold. The accurate calculation of interpulse relaxation requires knowledge of rate constants presently not well known; this is especially so for metal halide lasers.

  10. Process and composition for drying of gaseous hydrogen halides

    DOEpatents

    Tom, Glenn M.; Brown, Duncan W.

    1989-08-01

    A process for drying a gaseous hydrogen halide of the formula HX, wherein X is selected from the group consisting of bromine, chlorine, fluorine, and iodine, to remove water impurity therefrom, comprising: contacting the water impurity-containing gaseous hydrogen halide with a scavenger including a support having associated therewith one or more members of the group consisting of: (a) an active scavenging moiety selected from one or more members of the group consisting of: (i) metal halide compounds dispersed in the support, of the formula MX.sub.y ; and (ii) metal halide pendant functional groups of the formula -MX.sub.y-1 covalently bonded to the support, wherein M is a y-valent metal, and y is an integer whose value is from 1 to 3; (b) corresponding partially or fully alkylated compounds and/or pendant functional groups, of the metal halide compounds and/or pendant functional groups of (a); wherein the alkylated compounds and/or pendant functional groups, when present, are reactive with the gaseous hydrogen halide to form the corresponding halide compounds and/or pendant functional groups of (a); and M being selected such that the heat of formation, .DELTA.H.sub.f of its hydrated halide, MX.sub.y.(H.sub.2 O).sub.n, is governed by the relationship: .DELTA.H.sub.f .gtoreq.n.times.10.1 kilocalories/mole of such hydrated halide compound wherein n is the number of water molecules bound to the metal halide in the metal halide hydrate. Also disclosed is an appertaining scavenger composition and a contacting apparatus wherein the scavenger is deployed in a bed for contacting with the water impurity-containing gaseous hydrogen halide.

  11. Positron-alkali atom scattering

    NASA Technical Reports Server (NTRS)

    Mceachran, R. P.; Horbatsch, M.; Stauffer, A. D.; Ward, S. J.

    1990-01-01

    Positron-alkali atom scattering was recently investigated both theoretically and experimentally in the energy range from a few eV up to 100 eV. On the theoretical side calculations of the integrated elastic and excitation cross sections as well as total cross sections for Li, Na and K were based upon either the close-coupling method or the modified Glauber approximation. These theoretical results are in good agreement with experimental measurements of the total cross section for both Na and K. Resonance structures were also found in the L = 0, 1 and 2 partial waves for positron scattering from the alkalis. The structure of these resonances appears to be quite complex and, as expected, they occur in conjunction with the atomic excitation thresholds. Currently both theoretical and experimental work is in progress on positron-Rb scattering in the same energy range.

  12. Alkali metal/sulfur battery

    DOEpatents

    Anand, Joginder N.

    1978-01-01

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

  13. Superconductivity in alkali metal fullerides

    NASA Astrophysics Data System (ADS)

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

    1991-12-01

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

  14. Alkali metal sources for OLED devices

    NASA Astrophysics Data System (ADS)

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

    2005-07-01

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

  15. Making and Breaking of Lead Halide Perovskites.

    PubMed

    Manser, Joseph S; Saidaminov, Makhsud I; Christians, Jeffrey A; Bakr, Osman M; Kamat, Prashant V

    2016-02-16

    A new front-runner has emerged in the field of next-generation photovoltaics. A unique class of materials, known as organic metal halide perovskites, bridges the gap between low-cost fabrication and exceptional device performance. These compounds can be processed at low temperature (typically in the range 80-150 °C) and readily self-assemble from the solution phase into high-quality semiconductor thin films. The low energetic barrier for crystal formation has mixed consequences. On one hand, it enables inexpensive processing and both optical and electronic tunability. The caveat, however, is that many as-formed lead halide perovskite thin films lack chemical and structural stability, undergoing rapid degradation in the presence of moisture or heat. To date, improvements in perovskite solar cell efficiency have resulted primarily from better control over thin film morphology, manipulation of the stoichiometry and chemistry of lead halide and alkylammonium halide precursors, and the choice of solvent treatment. Proper characterization and tuning of processing parameters can aid in rational optimization of perovskite devices. Likewise, gaining a comprehensive understanding of the degradation mechanism and identifying components of the perovskite structure that may be particularly susceptible to attack by moisture are vital to mitigate device degradation under operating conditions. This Account provides insight into the lifecycle of organic-inorganic lead halide perovskites, including (i) the nature of the precursor solution, (ii) formation of solid-state perovskite thin films and single crystals, and (iii) transformation of perovskites into hydrated phases upon exposure to moisture. In particular, spectroscopic and structural characterization techniques shed light on the thermally driven evolution of the perovskite structure. By tuning precursor stoichiometry and chemistry, and thus the lead halide charge-transfer complexes present in solution, crystallization

  16. Mechanism and Selectivity in Nickel-Catalyzed Cross-Electrophile Coupling of Aryl Halides with Alkyl Halides

    PubMed Central

    Biswas, Soumik; Weix, Daniel J.

    2013-01-01

    The direct cross-coupling of two different electrophiles, such as an aryl halide with an alkyl halide, offers many advantages over conventional cross-coupling methods that require a carbon nucleophile. Despite its promise as a versatile synthetic strategy, a limited understanding of the mechanism and origin of cross selectivity has hindered progress in reaction development and design. Herein, we shed light on the mechanism for the nickel-catalyzed cross-electrophile coupling of aryl halides with alkyl halides and demonstrate that the selectivity arises from an unusual catalytic cycle that combines both polar and radical steps to form the new C-C bond. PMID:23952217

  17. Regenerable activated bauxite adsorbent alkali monitor probe

    DOEpatents

    Lee, Sheldon H. D.

    1992-01-01

    A regenerable activated bauxite adsorber alkali monitor probe for field applications to provide reliable measurement of alkali-vapor concentration in combustion gas with special emphasis on pressurized fluidized-bed combustion (PFBC) off-gas. More particularly, the invention relates to the development of a easily regenerable bauxite adsorbent for use in a method to accurately determine the alkali-vapor content of PFBC exhaust gases.

  18. Regenerable activated bauxite adsorbent alkali monitor probe

    DOEpatents

    Lee, S.H.D.

    1992-12-22

    A regenerable activated bauxite adsorber alkali monitor probe for field applications to provide reliable measurement of alkali-vapor concentration in combustion gas with special emphasis on pressurized fluidized-bed combustion (PFBC) off-gas. More particularly, the invention relates to the development of a easily regenerable bauxite adsorbent for use in a method to accurately determine the alkali-vapor content of PFBC exhaust gases. 6 figs.

  19. Controlling Metal-Halide Vapor Density in Lasers

    NASA Technical Reports Server (NTRS)

    Pivirotto, T. J.

    1984-01-01

    Streams of buffer gas convect and dilute metal-halide vapor. Technique uses flow of buffer gas through reservoir, which contains heated metal halide, to convect vapors into discharge tube. Second stream of buffer gas dilutes vapor. Final vapor density in laser tube controlled and changed by adjusting either one or both of buffer gas flow rates.

  20. [Emissions of methyl halides from coastal salt marshes: A review].

    PubMed

    Xie, Wen-xia; Zhao, Quan-sheng; Cui, Yu-qian; Du, Hui-na; Ye, Si-yuan

    2015-11-01

    Methyl halides are the major carrier of halogens in the atmosphere, and they play an important role in tropospheric and stratospheric ozone depletion. Meanwhile, methyl halides can act as greenhouse gases in the atmosphere, and they are also environmentally significant because of their toxicity. Coastal salt marshes, the important intertidal ecosystems at the land-ocean interface, have been considered to be a large potential natural source of methyl halides. In this paper, the research status of the natural source or sink of methyl halides, the mechanisms of their emission from coastal salt marshes and affecting factors were summarized. In view of this, the following research fields need to be strengthened in the future: 1) Long time-scale and large region-range researches about the emission of methyl halides and the evaluation of their source and sink function, 2) Accurate quantification of contribution rates of different plant species and various biological types to fluxes of methyl halides, 3) Further researches on effects of the tidal fluctuation process and flooding duration on methyl halides emission, 4) Effects of the global change and human activities on methyl halides emission. PMID:26915215

  1. How specific halide adsorption varies hydrophobic interactions.

    PubMed

    Stock, Philipp; Müller, Melanie; Utzig, Thomas; Valtiner, Markus

    2016-03-01

    Hydrophobic interactions (HI) are driven by the water structure around hydrophobes in aqueous electrolytes. How water structures at hydrophobic interfaces and how this influences the HI was subject to numerous studies. However, the effect of specific ion adsorption on HI and hydrophobic interfaces remains largely unexplored or controversial. Here, the authors utilized atomic force microscopy force spectroscopy at well-defined nanoscopic hydrophobic interfaces to experimentally address how specific ion adsorption of halide ions as well as NH4 (+), Cs(+), and Na(+) cations alters interaction forces across hydrophobic interfaces. Our data demonstrate that iodide adsorption at hydrophobic interfaces profoundly varies the hydrophobic interaction potential. A long-range and strong hydration repulsion at distances D > 3 nm, is followed by an instability which could be explained by a subsequent rapid ejection of adsorbed iodides from approaching hydrophobic interfaces. In addition, the authors find only a weakly pronounced influence of bromide, and as expected no influence of chloride. Also, all tested cations do not have any significant influence on HI. Complementary, x-ray photoelectron spectroscopy and quartz-crystal-microbalance with dissipation monitoring showed a clear adsorption of large halide ions (Br(-)/I(-)) onto hydrophobic self-assembled monolayers (SAMs). Interestingly, iodide can even lead to a full disintegration of SAMs due to specific and strong interactions of iodide with gold. Our data suggest that hydrophobic surfaces are not intrinsically charged negatively by hydroxide adsorption, as it was generally believed. Hydrophobic surfaces rather interact strongly with negatively charged large halide ions, leading to a surface charging and significant variation of interaction forces. PMID:26753786

  2. Ultraviolet absorption spectra of mercuric halides.

    NASA Technical Reports Server (NTRS)

    Templet, P.; Mcdonald, J. R.; Mcglynn, S. P.; Kendrow, C. H.; Roebber, J. L.; Weiss, K.

    1972-01-01

    The gas phase transitions of the mercuric halides were observed in the UV region by operating at temperatures above 400 K and at vapor pressures on the order of 0.5 mm. Spectral features exhibited by the chloride, bromide, and iodide of mercury correlate energetically with bands previously designated as intermolecular charge transfer transitions. The solution spectra of mercuric iodide and deep color of the crystals (if not due to some solid state interactions) indicate that this molecule may also have longer wavelength transitions.

  3. Raman spectra of hydroxide-halide melts

    NASA Astrophysics Data System (ADS)

    Zakiriyanova, I. D.; Khokhlov, V. A.

    2012-08-01

    The Raman spectra of molten binary mixtures based on sodium hydroxide and containing (mol %) 35 NaCl, 30 NaBr, and 30 NaI have been recorded at various temperatures. An increase in the vibrational frequency and the force constant of the O-H bond is detected under isothermal conditions upon a variation of the anionic composition of a melt in the series I → Br → Cl. Based on the experimental data, the viscosity of the hydroxide-halide melts is estimated.

  4. Alkali-Metal Spin Maser.

    PubMed

    Chalupczak, W; Josephs-Franks, P

    2015-07-17

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

  5. 10 CFR 429.54 - Metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 10 Energy 3 2012-01-01 2012-01-01 false Metal halide lamp ballasts and fixtures. 429.54 Section... CONSUMER PRODUCTS AND COMMERCIAL AND INDUSTRIAL EQUIPMENT Certification § 429.54 Metal halide lamp ballasts... are applicable to metal halide lamp ballasts; and (2) For each basic model of metal halide...

  6. 10 CFR 429.54 - Metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 10 Energy 3 2014-01-01 2014-01-01 false Metal halide lamp ballasts and fixtures. 429.54 Section... CONSUMER PRODUCTS AND COMMERCIAL AND INDUSTRIAL EQUIPMENT Certification § 429.54 Metal halide lamp ballasts... are applicable to metal halide lamp ballasts; and (2) For each basic model of metal halide...

  7. 10 CFR 429.54 - Metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 10 Energy 3 2013-01-01 2013-01-01 false Metal halide lamp ballasts and fixtures. 429.54 Section... CONSUMER PRODUCTS AND COMMERCIAL AND INDUSTRIAL EQUIPMENT Certification § 429.54 Metal halide lamp ballasts... are applicable to metal halide lamp ballasts; and (2) For each basic model of metal halide...

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

    PubMed Central

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

    2016-01-01

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

  9. Methyl halide production associated with kelp

    NASA Technical Reports Server (NTRS)

    Dastoor, Minoo N.; Manley, Steven L.

    1985-01-01

    Methyl halides (MeX) are important trace constituents of the atmosphere because they, mostly MeCl, have a major impact on the atmospheric ozone layer. Also, MeCl may account for 5 pct. of the total Cl budget and MeI may have a central role in the biogeochemical cycling of iodine. High MeI concentrations were found in seawater from kelp beds and it has been suggested that MeI is produced by kelps and that MeI and MeBr along with numerous other halocarbons were released by non-kelp marine macroalgae. The objective was to determine if kelps (and other seaweeds) are sources of MeX and to assess their contribution to the estimated global source strength (EGSS) of MeX. Although the production of MeX appears to be associated with kelp, microbes involved with kelp degradation also produce MeX. Microbial MeX production may be of global significance. The microbial MeX production potential, assuming annual kelp production equals kelp degradation and 100 pct. conversion of kelp halides to MeX, is approx. 2 x the EGSS. This is not achieved but indicates that microbial production of MeX may be of global significance.

  10. Finding new perovskite halides via machine learning

    DOE PAGESBeta

    Pilania, Ghanshyam; Balachandran, Prasanna V.; Kim, Chiho; Lookman, Turab

    2016-04-26

    Advanced materials with improved properties have the potential to fuel future technological advancements. However, identification and discovery of these optimal materials for a specific application is a non-trivial task, because of the vastness of the chemical search space with enormous compositional and configurational degrees of freedom. Materials informatics provides an efficient approach toward rational design of new materials, via learning from known data to make decisions on new and previously unexplored compounds in an accelerated manner. Here, we demonstrate the power and utility of such statistical learning (or machine learning, henceforth referred to as ML) via building a support vectormore » machine (SVM) based classifier that uses elemental features (or descriptors) to predict the formability of a given ABX3 halide composition (where A and B represent monovalent and divalent cations, respectively, and X is F, Cl, Br, or I anion) in the perovskite crystal structure. The classification model is built by learning from a dataset of 185 experimentally known ABX3 compounds. After exploring a wide range of features, we identify ionic radii, tolerance factor, and octahedral factor to be the most important factors for the classification, suggesting that steric and geometric packing effects govern the stability of these halides. As a result, the trained and validated models then predict, with a high degree of confidence, several novel ABX3 compositions with perovskite crystal structure.« less

  11. Finding New Perovskite Halides via Machine learning

    NASA Astrophysics Data System (ADS)

    Pilania, Ghanshyam; Balachandran, Prasanna V.; Kim, Chiho; Lookman, Turab

    2016-04-01

    Advanced materials with improved properties have the potential to fuel future technological advancements. However, identification and discovery of these optimal materials for a specific application is a non-trivial task, because of the vastness of the chemical search space with enormous compositional and configurational degrees of freedom. Materials informatics provides an efficient approach towards rational design of new materials, via learning from known data to make decisions on new and previously unexplored compounds in an accelerated manner. Here, we demonstrate the power and utility of such statistical learning (or machine learning) via building a support vector machine (SVM) based classifier that uses elemental features (or descriptors) to predict the formability of a given ABX3 halide composition (where A and B represent monovalent and divalent cations, respectively, and X is F, Cl, Br or I anion) in the perovskite crystal structure. The classification model is built by learning from a dataset of 181 experimentally known ABX3 compounds. After exploring a wide range of features, we identify ionic radii, tolerance factor and octahedral factor to be the most important factors for the classification, suggesting that steric and geometric packing effects govern the stability of these halides. The trained and validated models then predict, with a high degree of confidence, several novel ABX3 compositions with perovskite crystal structure.

  12. Process for the disposal of alkali metals

    DOEpatents

    Lewis, Leroy C.

    1977-01-01

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

  13. The alkali metals: 200 years of surprises.

    PubMed

    Dye, James L

    2015-03-13

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

  14. Tellurite glass as a waste form for mixed alkali-chloride waste streams: Candidate materials selection and initial testing

    NASA Astrophysics Data System (ADS)

    Riley, Brian J.; Rieck, Bennett T.; McCloy, John S.; Crum, Jarrod V.; Sundaram, S. K.; Vienna, John D.

    2012-05-01

    Tellurite glasses have historically been shown to host large concentrations of halides. They are here considered for the first time as a waste form for immobilizing chloride wastes, such as may be generated in the proposed molten alkali salt electrochemical separations step in nuclear fuel reprocessing. Key properties of several tellurite glasses are determined to assess acceptability as a chloride waste form. TeO2 glasses with other oxides (PbO, Al2O3 + B2O3, WO3, P2O5, or ZnO) were fabricated with and without 10 mass% of a simulated (non-radioactive) mixed alkali, alkaline-earth, and rare earth chloride waste. Measured chemical durability is compared for the glasses, as determined by the product consistency test (PCT), a common standardized chemical durability test often used to validate borosilicate glass waste forms. The glass with the most promise as a waste form is the TeO2-PbO system, as it offers good halide retention, a low sodium release (by PCT) comparable with high-level waste silicate glass waste forms, and a high storage density.

  15. Method of handling radioactive alkali metal waste

    DOEpatents

    Wolson, Raymond D.; McPheeters, Charles C.

    1980-01-01

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

  16. Method of handling radioactive alkali metal waste

    DOEpatents

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

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

  17. BEAM EXPOSURE DEPENDENCE AND MECHANISMS OF PHOTON-STIMULATED DESORPTION FROM ALKALI FLUORIDES

    SciTech Connect

    Parks, C.C.; Shirley, D.A.; Loubriel, G.

    1983-11-01

    Photon-stimulated desorption experiments were performed on the (001) face of LiF for photon energies near the F(2s) and Li(ls) edges (from 37 to 72 eV). There are structures in the F{sup +} yield above the F(2s) edge which are absent in the Li{sup +} spectrum, differences in detail in the Li{sup +} and F{sup +} yields near the Li(1s) edge, and considerable broadening of the desorption yields as compared to the bulk photoabsorption spectrum. The first observation of a strong x-ray, and visible, beam exposure dependence of ion yields from LiF and NaF is also presented. These results are discussed in terms of electronic and defect properties of alkali halides.

  18. OSL studies of alkali fluoroperovskite single crystals for radiation dosimetry

    NASA Astrophysics Data System (ADS)

    Daniel, D. Joseph; Raja, A.; Madhusoodanan, U.; Annalakshmi, O.; Ramasamy, P.

    2016-08-01

    This paper presents a preliminary investigation of the optically stimulated luminescence (OSL) of alkali fluoroperovskite single crystals for radiation dosimetry. The perovskite-like KMgF3, NaMgF3 and LiBaF3 polycrystalline compounds doped with rare earths (Eu2+ and Ce3+) were synthesized by standard solid state reaction technique. Phase purity of the synthesized compounds was analyzed by powder X-ray diffraction technique. Single crystals of these compounds have been grown from melt by using vertical Bridgman-Stockbarger method. The Linearly Modulated OSL and Continuous Wave OSL measurements were performed in these alkali fluorides using blue light stimulation. Thermal bleaching experiments have shown that OSL signals originate from traps which are unstable near 200 °C, thus proving the suitability of the signals for dosimetric purposes. Optical bleaching measurements were also performed for these fluoride samples. OSL dose response was studied as a function of dose which was found to increase with beta dose.

  19. Temperature dependence of nonlinear optical properties in Li doped nano-carbon bowl material

    NASA Astrophysics Data System (ADS)

    Li, Wei-qi; Zhou, Xin; Chang, Ying; Quan Tian, Wei; Sun, Xiu-Dong

    2013-04-01

    The mechanism for change of nonlinear optical (NLO) properties with temperature is proposed for a nonlinear optical material, Li doped curved nano-carbon bowl. Four stable conformations of Li doped corannulene were located and their electronic properties were investigated in detail. The NLO response of those Li doped conformations varies with relative position of doping agent on the curved carbon surface of corannulene. Conversion among those Li doped conformations, which could be controlled by temperature, changes the NLO response of bulk material. Thus, conformation change of alkali metal doped carbon nano-material with temperature rationalizes the variation of NLO properties of those materials.

  20. Adsorption of hydrated halide ions on charged electrodes: Molecular dynamics simulation

    NASA Astrophysics Data System (ADS)

    Glosli, James N.; Philpott, Michael R.

    1993-04-01

    Constant temperature molecular dynamics has been used to simulate the adsorption of hydrated halide ion X(-) = F(-), Cl(-), Br(-), and I(-), and lithium ion Li(+) on a flat uniformly charged surfaces. The simulations were done with either 214 water molecules and two ions (Li(+) and X(-)) in a box 2.362 nm deep or with 430 water molecules and the two ions in a box 4.320 nm deep. The boxes were periodically replicated in the xy directions. The magnitude of the surface charge on the box end was + or - 0.11 c/nm(sup 2), corresponding to an electric field of 2 x 10(exp 7) V/cm. The lateral dimensions of the simulation cell were 1.862 nm x 1.862 nm (x times y) in each case. All of the water molecules and ions interacted with the end walls via a weak 9 - 3 potential. The ST2 water model and parameters optimized for alkali halides interacting with the model ST2 water molecule were used in the calculations. Common practices of truncating the interactions at a finite distance (0.82 nm) and switching off Coulomb interactions at small distances were followed. The temperature was set at T = 2.411 kJ/mole (290 K). Some of the properties calculated were: distribution density profiles for ions and water across the gap important for comparisons iwth Gouy-Chapman theory, adsorbed ion-water pair correlation functions, the number of water molecules in the first and second hydration shells of the ions as a function of time. The time spent by a water molecule in the hydration shell was calculated to be approximately ten times longer for lithium than any other ion. The correlation between distance from the electrode and hydration number was studied and generally found to be pronounced for the larger anions.

  1. Halide-Substituted Electronic Properties of Organometal Halide Perovskite Films: Direct and Inverse Photoemission Studies.

    PubMed

    Li, Chi; Wei, Jian; Sato, Mikio; Koike, Harunobu; Xie, Zhong-Zhi; Li, Yan-Qing; Kanai, Kaname; Kera, Satoshi; Ueno, Nobuo; Tang, Jian-Xin

    2016-05-11

    Solution-processed perovskite solar cells are attracting increasing interest due to their potential in next-generation hybrid photovoltaic devices. Despite the morphological control over the perovskite films, quantitative information on electronic structures and interface energetics is of paramount importance to the optimal photovoltaic performance. Here, direct and inverse photoemission spectroscopies are used to determine the electronic structures and chemical compositions of various methylammonium lead halide perovskite films (MAPbX3, X = Cl, Br, and I), revealing the strong influence of halide substitution on the electronic properties of perovskite films. Precise control over halide compositions in MAPbX3 films causes the manipulation of the electronic properties, with a qualitatively blue shift along the I → Br → Cl series and showing the increase in ionization potentials from 5.96 to 7.04 eV and the change of transport band gaps in the range from 1.70 to 3.09 eV. The resulting light absorption of MAPbX3 films can cover the entire visible region from 420 to 800 nm. The results presented here provide a quantitative guide for the analysis of perovskite-based solar cell performance and the selection of optimal carrier-extraction materials for photogenerated electrons and holes. PMID:27101940

  2. Unraveling the Role of Monovalent Halides in Mixed-Halide Organic-Inorganic Perovskites.

    PubMed

    Deepa, Melepurath; Ramos, F Javier; Shivaprasad, S M; Ahmad, Shahzada

    2016-03-16

    The performance of perovskite solar cells is strongly influenced by the composition and microstructure of the perovskite. A recent approach to improve the power conversion efficiencies utilized mixed-halide perovskites, but the halide ions and their roles were not directly studied. Unraveling their precise location in the perovskite layer is of paramount importance. Here, we investigated four different perovskites by using X-ray photoelectron spectroscopy, and found that among the three studied mixed-halide perovskites, CH3 NH3 Pb(I0.74 Br0.26 )3 and CH3 NH3 PbBr3-x Clx show peaks that unambiguously demonstrate the presence of iodide and bromide in the former, and bromide and chloride in the latter. The CH3 NH3 PbI3-x Clx perovskite shows anomalous behavior, the iodide content far outweighs that of the chloride; a small proportion of chloride, in all likelihood, resides deep within the TiO2 /absorber layer. Our study reveals that there are many distinguishable structural differences between these perovskites, and that these directly impact the photovoltaic performances. PMID:26717046

  3. Vibrational Spectroscopy of Sodium Halide and Hydrogen Halide Aqueous Solutions: Application to Atmospheric Aerosol Chemistry

    NASA Astrophysics Data System (ADS)

    Levering, L. M.; Liu, D.; Allen, H. C.

    2003-12-01

    Heterogeneous reactions on the surfaces of atmospheric aerosols play an important role in atmospheric chemistry. These reactions are capable of converting alkyl and hydrogen halides (common constituents of marine boundary aerosols) into active halogen compounds. Fundamental questions still remain concerning surface species and reaction mechanisms pertaining to marine boundary aerosols. The first step in beginning to understand these heterogeneous reactions is to determine how ions in solution affect the structure of water at the interface. Vibrational sum frequency generation spectroscopy is used to examine the air-liquid interface of sodium halide and hydrogen halide (i.e. strong acid) solutions. In addition, comparison of the bulk water structure to that of the interface is accomplished using Raman spectroscopy. The hydrogen-bonding environment at the surface of NaCl is found to be similar to that of the air-water interface. In contrast, the interfacial water structure of NaBr, HCl, and HBr solutions is significantly altered from that of neat water. In the bulk, NaCl, NaBr, HCl, and HBr solutions disturb the hydrogen-bonding network of neat water. A comparison between the corresponding salts and acids show that the salts produce greater disorder (i.e. less coupling of the water symmetric stretching modes) in the bulk water structure.

  4. Alkali burns from wet cement.

    PubMed Central

    Peters, W. J.

    1984-01-01

    When water is added to the dry materials of Portland cement calcium hydroxide is formed; the wet cement is caustic (with a pH as high as 12.9) and can produce third-degree alkali burns after 2 hours of contact. Unlike professional cement workers, amateurs are usually not aware of any danger and may stand or kneel in the cement for long periods. As illustrated in a case report, general physicians may recognize neither the seriousness of the injury in its early stages nor the significance of a history of prolonged contact with wet cement. All people working with cement should be warned about its dangers and advised to immediately wash and dry the skin if contact does occur. Images Fig. 1 PMID:6561052

  5. Aqueous Copper(II) Photoinduced Polymerization of Acrylates: Low Copper Concentration and the Importance of Sodium Halide Salts.

    PubMed

    Jones, Glen R; Whitfield, Richard; Anastasaki, Athina; Haddleton, David M

    2016-06-15

    Photoinduced metal-mediated radical polymerization is a rapidly developing technique which allows for the synthesis of macromolecules with defined molecular weight and narrow molecular weight distributions, although typically exhibiting significant limitations in aqueous media. Herein we demonstrate that the presence of alkali metal halide salts, in conjunction with low copper concentration and UV irradiation, allows for the controlled polymerization of water-soluble acrylates in aqueous media, yielding narrow molecular weight distributions and high conversions. Despite the aqueous environment which typically compromises polymer end group fidelity, chain extensions have also been successfully performed and different degrees of polymerization were targeted. Importantly, no conversion was observed in the absence of UV light and the polymerization could be switched "on" and "off" upon demand, as demonstrated by intermittent light and dark periods and thus allowing access to spatiotemporal control. PMID:27184213

  6. Hydrophobic Organic Hole Transporters for Improved Moisture Resistance in Metal Halide Perovskite Solar Cells.

    PubMed

    Leijtens, Tomas; Giovenzana, Tommaso; Habisreutinger, Severin N; Tinkham, Jonathan S; Noel, Nakita K; Kamino, Brett A; Sadoughi, Golnaz; Sellinger, Alan; Snaith, Henry J

    2016-03-01

    Solar cells based on organic-inorganic perovskite semiconductor materials have recently made rapid improvements in performance, with the best cells performing at over 20% efficiency. With such rapid progress, questions such as cost and solar cell stability are becoming increasingly important to address if this new technology is to reach commercial deployment. The moisture sensitivity of commonly used organic-inorganic metal halide perovskites has especially raised concerns. Here, we demonstrate that the hygroscopic lithium salt commonly used as a dopant for the hole transport material in perovskite solar cells makes the top layer of the devices hydrophilic and causes the solar cells to rapidly degrade in the presence of moisture. By using novel, low cost, and hydrophobic hole transporters in conjunction with a doping method incorporating a preoxidized salt of the respective hole transporters, we are able to prepare efficient perovskite solar cells with greatly enhanced water resistance. PMID:26859777

  7. Metal halide perovskites for energy applications

    NASA Astrophysics Data System (ADS)

    Zhang, Wei; Eperon, Giles E.; Snaith, Henry J.

    2016-06-01

    Exploring prospective materials for energy production and storage is one of the biggest challenges of this century. Solar energy is one of the most important renewable energy resources, due to its wide availability and low environmental impact. Metal halide perovskites have emerged as a class of semiconductor materials with unique properties, including tunable bandgap, high absorption coefficient, broad absorption spectrum, high charge carrier mobility and long charge diffusion lengths, which enable a broad range of photovoltaic and optoelectronic applications. Since the first embodiment of perovskite solar cells showing a power conversion efficiency of 3.8%, the device performance has been boosted up to a certified 22.1% within a few years. In this Perspective, we discuss differing forms of perovskite materials produced via various deposition procedures. We focus on their energy-related applications and discuss current challenges and possible solutions, with the aim of stimulating potential new applications.

  8. The Renaissance of Halide Perovskites and Their Evolution as Emerging Semiconductors.

    PubMed

    Stoumpos, Constantinos C; Kanatzidis, Mercouri G

    2015-10-20

    The recent re-emergence of the halide perovskites, of the type AMX3, derives from a sea-changing breakthrough in the field of photovoltaics that has led to a whole new generation of solar devices with remarkable power conversion efficiency. The success in the field of photovoltaics has led to intense, combined research efforts to better understand these materials both from the fundamental chemistry and physics points of view and for the improvement of applied functional device engineering. This groundswell of activity has breathed new life into this long-known but largely "forgotten" class of perovskites. The impressive achievements of halide perovskites in photovoltaics, as well as other optoelectronic applications, stem from an unusually favorable combination of optical and electronic properties, with the ability to be solution processed into films. This defines them as a brand new class of semiconductors that can rival or exceed the performance of the venerable classes of III-V and II-IV semiconductors, which presently dominate the industries of applied optoelectronics. Our aim in this Account is to highlight the basic pillars that define the chemistry of the halide perovskites and their unconventional electronic properties through the prism of structure-property relationships. We focus on the synthetic requirements under which a halide perovskite can exist and emphasize how the synthetic conditions can determine the structural integrity and the bulk properties of the perovskites. Then we proceed to discuss the origins of the optical and electronic phenomena, using the perovskite crystal structure as a guide. Some of the most remarkable features of the perovskites dealt with in this Account include the evolution of a unique type of defect, which gives rise to superlattices. These can enhance or diminish the fluorescence properties of the perovskites. For example, the exotic self-doping ability of the Sn-based perovskites allows them to adopt electrical

  9. Rare-earth tri-halides methanol-adduct single-crystal scintillators for gamma ray and neutron detection

    NASA Astrophysics Data System (ADS)

    Boatner, L. A.; Wisniewski, D. J.; Neal, J. S.; Bell, Z. W.; Ramey, J. O.; Kolopus, J. A.; Chakoumakos, B. C.; Custelcean, R.; Wisniewska, M.; Pena, K. E.

    2009-08-01

    Cerium activated rare-earth tri- halides represent a well-known family of high performance inorganic rare-earth scintillators - including the high-light-yield, high-energy-resolution scintillator, cerium-doped lanthanum tribromide. These hygroscopic inorganic rare-earth halides are currently grown as single crystals from the melt - either by the Bridgman or Czochralski techniques - slow and expensive processes that are frequently characterized by severe cracking of the material due to anisotropic thermal stresses and cleavage effects. We have recently discovered a new family of cerium-activated rare-earth metal organic scintillators consisting of tri-halide methanol adducts of cerium and lanthanum - namely CeCl3(CH3OH)4 and LaBr3(CH3OH)4:Ce. These methanol-adduct scintillator materials can be grown near room temperature from a methanol solution, and their high solubility is consistent with the application of the rapid solution growth methods that are currently used to grow very large single crystals of potassium dihydrogen phosphate. The structures of these new rare-earth metal-organic scintillating compounds were determined by single crystal x-ray refinements, and their scintillation response to both gamma rays and neutrons, as presented here, was characterized using different excitation sources. Tri-halide methanol-adduct crystals activated with trivalent cerium apparently represent the initial example of a solution-grown rare-earth metal-organic molecular scintillator that is applicable to gamma ray, x-ray, and fast neutron detection.

  10. Integrating Sphere Alkali-Metal Vapor Cells

    NASA Astrophysics Data System (ADS)

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

    2010-03-01

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

  11. Alkali Silicate Vehicle Forms Durable, Fireproof Paint

    NASA Technical Reports Server (NTRS)

    Schutt, John B.; Seindenberg, Benjamin

    1964-01-01

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

  12. Diode pumped alkali vapor fiber laser

    DOEpatents

    Payne, Stephen A.; Beach, Raymond J.; Dawson, Jay W.; Krupke, William F.

    2007-10-23

    A method and apparatus is provided for producing near-diffraction-limited laser light, or amplifying near-diffraction-limited light, in diode pumped alkali vapor photonic-band-gap fiber lasers or amplifiers. Laser light is both substantially generated and propagated in an alkali gas instead of a solid, allowing the nonlinear and damage limitations of conventional solid core fibers to be circumvented. Alkali vapor is introduced into the center hole of a photonic-band-gap fiber, which can then be pumped with light from a pump laser and operated as an oscillator with a seed beam, or can be configured as an amplifier.

  13. Diode pumped alkali vapor fiber laser

    DOEpatents

    Payne, Stephen A.; Beach, Raymond J.; Dawson, Jay W.; Krupke, William F.

    2006-07-26

    A method and apparatus is provided for producing near-diffraction-limited laser light, or amplifying near-diffraction-limited light, in diode pumped alkali vapor photonic-band-gap fiber lasers or amplifiers. Laser light is both substantially generated and propagated in an alkali gas instead of a solid, allowing the nonlinear and damage limitations of conventional solid core fibers to be circumvented. Alkali vapor is introduced into the center hole of a photonic-band-gap fiber, which can then be pumped with light from a pump laser and operated as an oscillator with a seed beam, or can be configured as an amplifier.

  14. Advancements in flowing diode pumped alkali lasers

    NASA Astrophysics Data System (ADS)

    Pitz, Greg A.; Stalnaker, Donald M.; Guild, Eric M.; Oliker, Benjamin Q.; Moran, Paul J.; Townsend, Steven W.; Hostutler, David A.

    2016-03-01

    Multiple variants of the Diode Pumped Alkali Laser (DPAL) have recently been demonstrated at the Air Force Research Laboratory (AFRL). Highlights of this ongoing research effort include: a) a 571W rubidium (Rb) based Master Oscillator Power Amplifier (MOPA) with a gain (2α) of 0.48 cm-1, b) a rubidium-cesium (Cs) Multi-Alkali Multi-Line (MAML) laser that simultaneously lases at both 795 nm and 895 nm, and c) a 1.5 kW resonantly pumped potassium (K) DPAL with a slope efficiency of 50%. The common factor among these experiments is the use of a flowing alkali test bed.

  15. Electronic and Ionic Transport Dynamics in Organolead Halide Perovskites.

    PubMed

    Li, Dehui; Wu, Hao; Cheng, Hung-Chieh; Wang, Gongming; Huang, Yu; Duan, Xiangfeng

    2016-07-26

    Ion migration has been postulated as the underlying mechanism responsible for the hysteresis in organolead halide perovskite devices. However, the electronic and ionic transport dynamics and how they impact each other in organolead halide perovskites remain elusive to date. Here we report a systematic investigation of the electronic and ionic transport dynamics in organolead halide perovskite microplate crystals and thin films using temperature-dependent transient response measurements. Our study reveals that thermally activated ionic and electronic conduction coexist in perovskite devices. The extracted activation energies suggest that the electronic transport is easier, but ions migrate harder in microplates than in thin films, demonstrating that the crystalline quality and grain boundaries can fundamentally modify electronic and ionic transport in perovskites. These findings offer valuable insight on the electronic and ionic transport dynamics in organolead halide perovskites, which is critical for optimizing perovskite devices with reduced hysteresis and improved stability and efficiency. PMID:27315525

  16. Synergistic capture mechanisms for alkali and sulfur species from combustion. Final report

    SciTech Connect

    Peterson, T.W.; Shadman, F.; Wendt, J.O.L.; Mwabe, P.O.

    1994-02-01

    Experimental work was carried out on a 17 kW, 600 cm long, gas laboratory combustor, to investigate the post flame reactive capture of alkali species by kaolinite. Emphasis was on alkali/sorbent interactions occurring in flue gas at temperatures above the alkali dewpoint and on the formation of water insoluble reaction products. Time-temperature studies were carried out by injecting kaolinite at different axial points along the combustor. The effect of chlorine and sulfur on alkali capture was investigated by doping the flame with SO{sub 2} and Cl{sub 2} gases to simulate coal flame environments. Particle time and temperature history was kept as close as possible to that which would ordinarily be found in a practical boiler. Experiments designed to extract apparent initial reaction rates were carried using a narrow range, 1-2 {mu}m modal size sorbent, while, a coarse, multi size sorbent was used to investigate the governing transport mechanisms. The capture reaction has been proposed to be between alkali hydroxide and activated kaolinite, and remains so in the presence of sulfur and chlorine. The presence of sulfur reduces sodium capture by under 10% at 1300{degree}C. Larger reductions at lower temperatures are attributed to the elevated dewpoint of sodium ({approximately}850{degree}C) with subsequent reduction in sorbent residence time in the alkali gas phase domain. Chlorine reduces sodium capture by 30% across the temperature range covered by the present experiments. This result has been linked to thermodynamic equilibria between sodium hydroxide, sodium chloride and water.

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

    SciTech Connect

    Henning, R.

    1998-03-27

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

  18. Alkali metal for ultraviolet band-pass filter

    NASA Technical Reports Server (NTRS)

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

    1993-01-01

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

  19. Alkali Metal Handling Practices at NASA MSFC

    NASA Technical Reports Server (NTRS)

    Salvail, Patrick G.; Carter, Robert R.

    2002-01-01

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

  20. Alkali-metal intercalation in carbon nanotubes

    NASA Astrophysics Data System (ADS)

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

    1999-09-01

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

  1. Alkali metal intercalates of molybdenum disulfide.

    NASA Technical Reports Server (NTRS)

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

    1973-01-01

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

  2. Desulfurizing Coal With an Alkali Treatment

    NASA Technical Reports Server (NTRS)

    Ravindram, M.; Kalvinskas, J. J.

    1987-01-01

    Experimental coal-desulfurization process uses alkalies and steam in fluidized-bed reactor. With highly volatile, high-sulfur bituminous coal, process removed 98 percent of pyritic sulfur and 47 percent of organic sulfur. Used in coal liquefaction and in production of clean solid fuels and synthetic liquid fuels. Nitrogen or steam flows through bed of coal in reactor. Alkalies react with sulfur, removing it from coal. Nitrogen flow fluidizes bed while heating or cooling; steam is fluidizing medium during reaction.

  3. Analysis of the physical atomic forces between noble gas atoms, alkali ions and halogen ions

    NASA Technical Reports Server (NTRS)

    Wilson, J. W.; Heinbockel, J. H.; Outlaw, R. A.

    1986-01-01

    The physical forces between atoms and molecules are important in a number of processes of practical importance, including line broadening in radiative processes, gas and crystal properties, adhesion, and thin films. The components of the physical forces between noble gas atoms, alkali ions, and halogen ions are analyzed and a data base for the dispersion forces is developed from the literature based on evaluations with the harmonic oscillator dispersion model for higher order coefficients. The Zener model of the repulsive core is used in the context of the recent asymptotic wave functions of Handler and Smith; and an effective ionization potential within the Handler and Smith wave functions is defined to analyze the two body potential data of Waldman and Gordon, the alkali-halide molecular data, and the noble gas crystal and salt crystal data. A satisfactory global fit to this molecular and crystal data is then reproduced by the model to within several percent. Surface potentials are evaluated for noble gas atoms on noble gas and salt crystal surfaces with surface tension neglected. Within this context, the noble gas surface potentials on noble gas and salt crystals are considered to be accurate to within several percent.

  4. Density functional studies on hydrogen-bonded clusters of hydrogen halides and the interaction on halide anions

    NASA Astrophysics Data System (ADS)

    Nirmala, V.; Kolandaivel, P.

    Density functional theory (DFT) calculations have been performed to study the structures and stability of X-·(HX)n=2-5 clusters where X = F, Cl, Br at B3LYP/6-311++G** level of theory. The presence of halide ions in these clusters disintegrates the hydrogen halide clusters. All the hydrogen halides are then hydrogen bonded to the centrally placed halide ions, thereby forming multiple hydrogen bonds. The interaction energies have been corrected for the basis set superposition error (BSSE) using Boy's counterpoise correction method. Evidence for the destruction of hydrogen bonds in hydrogen halide clusters due to the presence of halide ions is further obtained from topological analysis and natural bond orbital analysis. The chemical hardness and chemical potential have been calculated for all the anion clusters. The above analysis reveals that hydrogen bonding in these systems is not an essentially electrostatic interaction. The nature of the stabilization interactions operative in these multiple hydrogen-bonded clusters has been explained in terms of many-body contribution to interaction energies. From these studies, an attempt has been made to understand the nature of the molecular properties resulting from different electronegativities of the halogens.

  5. Alkali metal crystalline polymer electrolytes.

    PubMed

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

    2009-07-01

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

  6. Infrared Spectra of Simple Inorganic Ion Pairs in Solid Solution: A Physical Inorganic Chemistry Experiment.

    ERIC Educational Resources Information Center

    Miller, Philip J.; Tong, William G.

    1980-01-01

    Presents a physical inorganic experiment in which large single crystals of the alkali halides doped with divalent ion impurities are prepared easily. Demonstrates the ion pairing of inorganic ions in solid solution. (CS)

  7. On the Electron Paramagnetic Resonance Studies in Mixed Alkali Borate Glasses

    SciTech Connect

    Padmaja, G.; Reddy, T. Goverdhan; Kistaiah, P.

    2011-10-20

    Mixed alkali effect in oxide based glasses is one of the current research activity and studies on the behavior of spectroscopic parameters in these systems are quite important to understand the basic nature of this phenomenon. EPR studies of mixed alkali glasses Li{sub 2}O-K{sub 2}O-ZnO-B{sub 2}O{sub 3} doped with Fe{sup 3+} and Mn{sup 2+} were carried out at room temperature. The EPR spectra show typical resonances of d{sup 5} system (Fe{sup 3+} and Mn{sup 2+}) in all the measured glass specimens. Evaluated hyperfine constant, number of paramagnetic centers and paramagnetic susceptibility values show deviation from the linearity with the progressive substitution of the Li ion with K in glass network.

  8. Color silver halide hologram production and mastering

    NASA Astrophysics Data System (ADS)

    Bjelkhagen, Hans I.; Huang, Qiang

    1997-04-01

    Color reflection holograms recorded with the Denisyuk geometry have been demonstrated by the recently formed HOLOS Corporation in New Hampshire. The Slavich red-green-blue (RGB) sensitized ultra-high resolution silver halide emulsion was used for the hologram recording. The employed laser wavelengths were 647 nm, 532 nm, and 476 nm, generated by an argon ion, a frequency doubled Nd:YAG, and a krypton ion laser, respectively. A beam combination mechanism with dichroic filters enabled a simultaneous RGB exposure, which made the color balance and overall exposure energy easy to control as well as simplifying the recording procedure. HOLOS has been producing limited edition color holograms in various sizes from 4' X 5' to 12' X 16'. A 30 foot long optical table and high power lasers will enable HOLOS to record color holograms up to the size of one meter square in the near future. Various approaches have been investigated in generating color hologram masters which have sufficiently high diffraction efficiency to contact copy the color images onto photopolymer materials. A specially designed test object including the 1931 CIE chromaticity diagram, a rainbow ribbon cable, pure yellow dots, and a cloisonne elephant was used for color recording experiments. In addition, the Macbeth Color Checker chart was used. Both colorimetric evaluation and scattering noise measurements were performed using the PR-650 Photo Research SpectraScan SpectraCalorimeter.

  9. Genetic Control of Methyl Halide Production in Arabidopsis

    NASA Astrophysics Data System (ADS)

    Rhew, R. C.; Ostergaard, L.; Saltzman, E. S.; Yanofsky, M. F.

    2003-12-01

    Methyl chloride and methyl bromide are the primary carriers of natural chlorine and bromine to the stratosphere where they catalyze the destruction of ozone, whereas methyl iodide influences aerosol formation and ozone loss in the troposphere. Methyl bromide is also an agricultural fumigant whose use is scheduled to be phased out by international agreement. Despite the economic and environmental importance of these methyl halides, their natural sources and biological production mechanisms are poorly understood. Currently identified sources include oceans, biomass burning, industrial and agricultural use, fuel combustion, salt marshes, wetlands, rice paddies, certain terrestrial plants and fungi, and abiotic processes. We demonstrate that the model plant Arabidopsis thaliana produces and emits methyl halides and that the enzyme primarily responsible for the production is encoded by the HARMLESS TO OZONE LAYER (HOL) gene located on chromosome II. In mutant plants that have a disruption of the HOL gene, methyl halide production is largely eliminated. A phylogenetic analysis using the HOL gene suggests that the ability to produce methyl halides is widespread among vascular plants. This approach provides a genetic basis for understanding and predicting patterns of methyl halide production by plants.

  10. Halide Perovskites: Poor Man's High-Performance Semiconductors.

    PubMed

    Stoumpos, Constantinos C; Kanatzidis, Mercouri G

    2016-07-01

    Halide perovskites are a rapidly developing class of medium-bandgap semiconductors which, to date, have been popularized on account of their remarkable success in solid-state heterojunction solar cells raising the photovoltaic efficiency to 20% within the last 5 years. As the physical properties of the materials are being explored, it is becoming apparent that the photovoltaic performance of the halide perovskites is just but one aspect of the wealth of opportunities that these compounds offer as high-performance semiconductors. From unique optical and electrical properties stemming from their characteristic electronic structure to highly efficient real-life technological applications, halide perovskites constitute a brand new class of materials with exotic properties awaiting discovery. The nature of halide perovskites from the materials' viewpoint is discussed here, enlisting the most important classes of the compounds and describing their most exciting properties. The topics covered focus on the optical and electrical properties highlighting some of the milestone achievements reported to date but also addressing controversies in the vastly expanding halide perovskite literature. PMID:27174223

  11. Two Dimensional Organometal Halide Perovskite Nanorods with Tunable Optical Properties.

    PubMed

    Aharon, Sigalit; Etgar, Lioz

    2016-05-11

    Organo-metal halide perovskite is an efficient light harvester in photovoltaic solar cells. Organometal halide perovskite is used mainly in its "bulk" form in the solar cell. Confined perovskite nanostructures could be a promising candidate for efficient optoelectronic devices, taking advantage of the superior bulk properties of organo-metal halide perovskite, as well as the nanoscale properties. In this paper, we present facile low-temperature synthesis of two-dimensional (2D) lead halide perovskite nanorods (NRs). These NRs show a shift to higher energies in the absorbance and in the photoluminescence compared to the bulk material, which supports their 2D structure. X-ray diffraction (XRD) analysis of the NRs demonstrates their 2D nature combined with the tetragonal 3D perovskite structure. In addition, by alternating the halide composition, we were able to tune the optical properties of the NRs. Fast Fourier transform, and electron diffraction show the tetragonal structure of these NRs. By varying the ligands ratio (e.g., octylammonium to oleic acid) in the synthesis, we were able to provide the formation mechanism of these novel 2D perovskite NRs. The 2D perovskite NRs are promising candidates for a variety of optoelectronic applications, such as light-emitting diodes, lasing, solar cells, and sensors. PMID:27089497

  12. Regeneration of zinc halide catalyst used in the hydrocracking of polynuclear hydrocarbons

    DOEpatents

    Gorin, Everett

    1978-01-01

    Improved recovery of spent molten zinc halide hydro-cracking catalyst is achieved in the oxidative vapor phase regeneration thereof by selective treatment of the zinc oxide carried over by the effluent vapors from the regeneration zone with hydrogen halide gas under conditions favoring the reaction of the zinc oxide with the hydrogen halide, whereby regenerated zinc halide is recovered in a solids-free state with little loss of zinc values.

  13. Halide-stabilized LiBH4, a room-temperature lithium fast-ion conductor.

    PubMed

    Maekawa, Hideki; Matsuo, Motoaki; Takamura, Hitoshi; Ando, Mariko; Noda, Yasuto; Karahashi, Taiki; Orimo, Shin-ichi

    2009-01-28

    Solid state lithium conductors are attracting much attention for their potential applications to solid-state batteries and supercapacitors of high energy density to overcome safety issues and irreversible capacity loss of the currently commercialized ones. Recently, we discovered a new class of lithium super ionic conductors based on lithium borohydride (LiBH(4)). LiBH(4) was found to have conductivity as high as 10(-2) Scm(-1) accompanied by orthorhombic to hexagonal phase transition above 115 degrees C. Polarization to the lithium metal electrode was shown to be extremely low, providing a versatile anode interface for the battery application. However, the high transition temperature of the superionic phase has limited its applications. Here we show that a chemical modification of LiBH(4) can stabilize the superionic phase even below room temperature. By doping of lithium halides, high conductivity can be obtained at room temperature. Both XRD and NMR confirmed room-temperature stabilization of superionic phase for LiI-doped LiBH(4). The electrochemical measurements showed a great advantage of this material as an extremely lightweight lithium electrolyte for batteries of high energy density. This material will open alternative opportunities for the development of solid ionic conductors other than previously known lithium conductors. PMID:19119813

  14. Structural phase transitions of barium halide nanocrystals in fluorozirconate glasses studied by Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Pfau, C.; Bohley, C.; Miclea, P.-T.; Schweizer, S.

    2011-04-01

    Rare-earth-doped fluorochlorozirconate (FCZ) and fluorobromozirconate (FBZ) glasses developed for fluorescence applications are analyzed, with particular attention paid to their phonon energy spectra. After thermal processing of as-made Eu-doped FCZ and FBZ glasses, Raman measurements show additional phonon bands at low phonon energies, indicating the formation of BaCl2 and BaBr2 nanocrystals, respectively. The phonon bands can be assigned to hexagonal, orthorhombic, or a mixture of both phases of BaCl2 and BaBr2 depending on the annealing conditions. Apart from line broadening, the Raman spectra of the orthorhombic nanocrystals agree well with those of BaCl2 and BaBr2 bulk crystals, while the metastable hexagonal phases of BaCl2 and BaBr2 are investigated only in appropriately treated FCZ and FBZ glasses, respectively. The experimental Raman spectra are compared to first principle studies of the phonon frequencies of the hexagonal and orthorhombic phases of both barium halides, showing good agreement.

  15. 10 CFR 431.322 - Definitions concerning metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 10 Energy 3 2010-01-01 2010-01-01 false Definitions concerning metal halide lamp ballasts and... FOR CERTAIN COMMERCIAL AND INDUSTRIAL EQUIPMENT Metal Halide Lamp Ballasts and Fixtures § 431.322 Definitions concerning metal halide lamp ballasts and fixtures. Ballast efficiency means, in the case of...

  16. 10 CFR 431.322 - Definitions concerning metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 10 Energy 3 2012-01-01 2012-01-01 false Definitions concerning metal halide lamp ballasts and fixtures. 431.322 Section 431.322 Energy DEPARTMENT OF ENERGY ENERGY CONSERVATION ENERGY EFFICIENCY PROGRAM FOR CERTAIN COMMERCIAL AND INDUSTRIAL EQUIPMENT Metal Halide Lamp Ballasts and Fixtures § 431.322 Definitions concerning metal halide...

  17. 10 CFR 431.322 - Definitions concerning metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 10 Energy 3 2013-01-01 2013-01-01 false Definitions concerning metal halide lamp ballasts and fixtures. 431.322 Section 431.322 Energy DEPARTMENT OF ENERGY ENERGY CONSERVATION ENERGY EFFICIENCY PROGRAM FOR CERTAIN COMMERCIAL AND INDUSTRIAL EQUIPMENT Metal Halide Lamp Ballasts and Fixtures § 431.322 Definitions concerning metal halide...

  18. 10 CFR 431.322 - Definitions concerning metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 10 Energy 3 2011-01-01 2011-01-01 false Definitions concerning metal halide lamp ballasts and fixtures. 431.322 Section 431.322 Energy DEPARTMENT OF ENERGY ENERGY CONSERVATION ENERGY EFFICIENCY PROGRAM FOR CERTAIN COMMERCIAL AND INDUSTRIAL EQUIPMENT Metal Halide Lamp Ballasts and Fixtures § 431.322 Definitions concerning metal halide...

  19. 40 CFR 721.10181 - Halide salt of an alkylamine (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halide salt of an alkylamine (generic... Specific Chemical Substances § 721.10181 Halide salt of an alkylamine (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halide salt...

  20. 40 CFR 721.10181 - Halide salt of an alkylamine (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Halide salt of an alkylamine (generic... Specific Chemical Substances § 721.10181 Halide salt of an alkylamine (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halide salt...

  1. 40 CFR 721.10181 - Halide salt of an alkylamine (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Halide salt of an alkylamine (generic... Specific Chemical Substances § 721.10181 Halide salt of an alkylamine (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halide salt...

  2. 40 CFR 721.10181 - Halide salt of an alkylamine (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Halide salt of an alkylamine (generic... Specific Chemical Substances § 721.10181 Halide salt of an alkylamine (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halide salt...

  3. DFT STUDY OF HYDROGEN STORAGE ON Li- AND Na-DOPED C59B HETEROFULLERENE

    NASA Astrophysics Data System (ADS)

    Zahedi, Ehsan; Mozaffari, Majid

    2014-05-01

    Effect of light alkali metal (Li and Na) decorated on the C59B heterofullerene for hydrogen storage is considered using DFT-MPW1PW91 method. Results show that Li and Na atoms strongly prefer to adsorb on top of five-member and six-member ring where a carbon atom is replaced by a boron atom. Significant charge transfer from the alkali metal to the C59B compensates for the electron deficiency of C59B and makes the latter aromatic in nature. Corrected binding energies of hydrogen molecule on the alkali-doped C59B using counterpoise method, structural properties and NBO analysis indicate that first hydrogen molecule is adsorbed physically and does not support minimal conditions of DOE requirement. Finally, positive values of binding energies for the adsorption of a second hydrogen molecule show that alkali doped C59B are capable of storing a maximum of one hydrogen molecule.

  4. Alkali metal adsorption on Al(111)

    NASA Astrophysics Data System (ADS)

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

    1993-06-01

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

  5. SAFE Alkali Metal Heat Pipe Reliability

    NASA Astrophysics Data System (ADS)

    Reid, Robert S.

    2003-01-01

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

  6. Qualifying composition dependent p and n self-doping in CH3NH3PbI3

    NASA Astrophysics Data System (ADS)

    Wang, Qi; Shao, Yuchuan; Xie, Haipeng; Lyu, Lu; Liu, Xiaoliang; Gao, Yongli; Huang, Jinsong

    2014-10-01

    We report the observation of self-doping in perovskite. CH3NH3PbI3 was found to be either n- or p-doped by changing the ratio of methylammonium halide (MAI) and lead iodine (PbI2) which are the two precursors for perovskite formation. MAI-rich and PbI2-rich perovskite films are p and n self-doped, respectively. Thermal annealing can convert the p-type perovskite to n-type by removing MAI. The carrier concentration varied as much as six orders of magnitude. A clear correlation between doping level and device performance was also observed.

  7. The mixed alkali effect in zinc-compensated (K,Na)-β-gallate

    NASA Astrophysics Data System (ADS)

    Chandrashekhar, G. V.; Foster, L. M.

    1982-03-01

    The "mixed alkali effect" was investigated in a Zn-doped K-β-gallate fast ion conductor with partial replacement of the K by Na. A minimum in conductivity occurs at about 0.8 atom fraction Na. A model is proposed in which the site occupancies are determined by the interstitial pair concept, and the conductivity minimum occurs when Beevers-Ross sites are occupied by K + only. A knee in the Arrhenius plots of samples containing potassium is explained as the onset of activation of K + away from interstitial complexes bound coulombically to the zinc charge-compensating centers.

  8. Diode pumped alkali lasers (DPALs): an overview

    NASA Astrophysics Data System (ADS)

    Krupke, William F.

    2008-05-01

    The concept of power-scalable, high beam-quality diode pumped alkali lasers was introduced in 2003 [Krupke, US Patent No. 6,643,311; Opt. Letters, 28, 2336 (2003)]. Since then several laboratory DPAL devices have been reported on, confirming many of the spectroscopic, kinetic, and laser characteristics projected from literature data. This talk will present an overview of the DPAL concept, summarize key relevant properties of the cesium, rubidium, and potassium alkali vapor gain media so-far examined, outline power scaling considerations, and highlight results of published DPAL laboratory experiments.

  9. Alkali metal vapors - Laser spectroscopy and applications

    NASA Technical Reports Server (NTRS)

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

    1980-01-01

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

  10. Ultrafast time-resolved spectroscopy of lead halide perovskite films

    NASA Astrophysics Data System (ADS)

    Idowu, Mopelola A.; Yau, Sung H.; Varnavski, Oleg; Goodson, Theodore

    2015-09-01

    Recently, lead halide perovskites which are organic-inorganic hybrid structures, have been discovered to be highly efficient as light absorbers. Herein, we show the investigation of the excited state dynamics and emission properties of non-stoichiometric precursor formed lead halide perovskites grown by interdiffusion method using steady-state and time-resolved spectroscopic measurements. The influence of the different ratios of the non-stoichiometric precursor solution was examined. The observed photoluminescence properties were correlated with the femtosecond transient absorption measurements.

  11. Thermodynamic reactivity, growth and characterization of mercurous halide crystals

    NASA Technical Reports Server (NTRS)

    Singh, N. B.; Gottlieb, M.; Henningsen, T.; Hopkins, R. H.; Mazelsky, R.; Singh, M.; Glicksman, M. E.; Paradies, C.

    1992-01-01

    Thermodynamic calculations were carried out for the Hg-X-O system (X = Cl, Br, I) to identify the potential sources of contamination and relative stability of oxides and oxy-halide phases. The effect of excess mercury vapor pressure on the optical quality of mercurous halide crystal was studied by growing several mercurous chloride crystals from mercury-rich composition. The optical quality of crystals was examined by birefringence interferometry and laser scattering studies. Crystals grown in slightly mercury-rich composition showed improved optical quality relative to stoichiometric crystals.

  12. Thallous halide materials for use in cryogenic applications

    NASA Technical Reports Server (NTRS)

    Lawless, William N. (Inventor)

    1981-01-01

    Thallous halides, either alone or in combination with other ceramic materials, are used in cryogenic applications such as heat exchange material for the regenerator section of a closed-cycle cryogenic refrigeration section, as stabilizing coatings for superconducting wires, and as dielectric insulating materials. The thallous halides possess unusually large specific heats at low temperatures, have large thermal conductivities, are nonmagnetic, and are nonconductors of electricity. They can be formed into a variety of shapes such as spheres, bars, rods, or the like and can be coated onto substrates.

  13. Boron and aluminum halides under pressure - polymerization and chemical transformations

    NASA Astrophysics Data System (ADS)

    Yao, Yansun

    2013-06-01

    High-pressure phase transitions of boron and aluminum halides have been theoretically studied. At low pressure, crystals of the familiar monomers (BX3) and dimers (Al2X6) are the structures of choice. While the higher oligomers as well as three dimensional infinite polymers are unstable at ambient pressure, they are stabilized by application of external pressure, taking advantage of the extra orbitals made accessible by the increased coordination. Several new crystal structures of boron and aluminum halides have been predicted at high pressures. Calculated x-ray diffraction patterns and Raman spectra of these phases are in good agreement with available experimental data.

  14. Applications of Raman scattering spectroscopy to halide glasses

    NASA Astrophysics Data System (ADS)

    Bendow, B.; Banerjee, P. K.; Drexhage, M. G.

    1983-04-01

    Polarized Raman scattering spectroscopy is a useful tool for investigating fundamental vibrational properties, structure and bonding, origins of IR edge absorption, and dispersion of the IR refractive index. In this paper, the application of Raman spectroscopy to halide glasses and, in particular, heavy metal fluoride glasses, is described. The spectra of the latter differ substantially from those of simple oxide, halide or chalcogenide glasses and, moreover, display a wide range of vibrational characteristics, depending on composition. In combination with infrared spectroscopy, useful guidelines can be developed for tailoring glass compositions for specific applications.

  15. Alkali-aggregate reaction in concrete containing high-alkali cement and granite aggregate

    SciTech Connect

    Owsiak, Z

    2004-01-01

    The paper discusses results of the research into the influence of high-alkali Portland cement on granite aggregate. The deformation of the concrete structure occurred after 18 months. The research was carried out by means of a scanning electron microscope equipped with a high-energy dispersive X-ray analyzer that allowed observation of unpolished sections of concrete bars exhibiting the cracking pattern typical of the alkali-silica reaction. Both the microscopic observation and the X-ray elemental analysis confirm the presence of alkali-silica gel and secondary ettringite in the cracks.

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

    DOEpatents

    Soung, W.Y.

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

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

    DOEpatents

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

    1978-01-01

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

  18. Quantum efficiencies of imaging detectors with alkali halide photocathodes. I - Microchannel plates with separate and integral CsI photocathodes

    NASA Technical Reports Server (NTRS)

    Carruthers, George R.

    1987-01-01

    Measurements and comparisons have been made of the quantum efficiencies of microchannel plate (MCP) detectors in the far-UV (below 2000-A) wavelength range using CsI photocathodes (a) deposited on the front surfaces of microchannel plates and (b) deposited on solid substrates as opaque photocathodes with the resulting photoelectrons input to microchannel plates. The efficiences were measured in both pulse-counting and photodiode modes of operation. Typical efficiencies are about 15 percent at 1216 A for a CsI-coated MCP compared with 65 percent for an opaque CsI photocathode MCP detector. Special processing has yielded an efficiency as high as 20 percent for a CsI-coated MCP. This may possibly be further improved by optimization of the tilt angle of the MCP channels relative to the front face of the MCP and incident radiation. However, at present there still remains a factor of at least 3 quantum efficiency advantage in the separate opaque CsI photocathode configuration.

  19. Cocrystallization of certain 4f and 5f elements in the bivalent state with alkali metal halides

    SciTech Connect

    Mikheev, N.B.; Kamenskaya, A.M.; Veleshko, I.E.; Kulyukhin, S.A.

    1987-01-01

    The cocrystallization of Fm/sup 2 +/, Es/sup 2 +/, Cf/sup 2 +/, Am/sup 2 +/, Yb/sup 2 +/, Eu/sup 2 +/ and Sr/sup 2 +/ with NaCl, KCl and KBr in tetrahydrofuran (THF), hexamethylphosphorotriamide (HMPA), and ethanol has been studied. It is shown that in water-ethanol medium An/sup 2 +/ cocrystallize with KCl by the formation of anomalous mixed crystals and Ln/sup 2 +/ do not cocrystallize. In HMPA neither Ln/sup 2 +/ nor An/sup 2 +/ are observed to transfer into the KBr solid phase, while in THF both Ln/sup 2 +/ and An/sup 2 +/ cocrystallize with NaCl. The change in the behavior on Ln/sup 2 +/ and An/sup 2 +/ cocrystallize with a change from one solvent to another is caused by the difference in the effective ionic radii of these elements, which arises from the large nephelauxetic effect for An/sup 2 +/ as well as by the different solvating power of these solvents.

  20. The interaction energies and polarizabilities of sodium fluoride, sodium chloride, and some alkali and halide ions pairs

    NASA Astrophysics Data System (ADS)

    Bounds, David G.; Hinchliffe, Alan

    1982-02-01

    Ab initio SCF pair potentials and polarizabilities for NaF, NaCl, F 2-2, Na 2-2, K 2-2, FCl 2-, LiNa 2+, LiK 2+, presented. Together with results reported previously, these values form a complete and consistent set of energy and polarizability data on the fluorides and chlorides of lithium, sodium and potassium.

  1. On the 2 s-like relaxed excited state of the F center in alkali halide crystals

    NASA Astrophysics Data System (ADS)

    Panov, V. G.; Varaksin, A. N.; Sobolev, A. B.

    2008-06-01

    The energy and spectroscopic characteristics of the first excited 2 s-like electron state of the F center are presented according to the calculations performed in the framework of the variational model proposed by Gourary and Adrian. The relaxation of the crystal lattice in the vicinity of the excited F center is described. The problem of the spatial propagation of the F center is discussed. The results obtained for the 2 p and 2 s states of the F center are compared with each other and with the relevant experimental data.

  2. Airplane dopes and doping

    NASA Technical Reports Server (NTRS)

    Smith, W H

    1919-01-01

    Cellulose acetate and cellulose nitrate are the important constituents of airplane dopes in use at the present time, but planes were treated with other materials in the experimental stages of flying. The above compounds belong to the class of colloids and are of value because they produce a shrinking action on the fabric when drying out of solution, rendering it drum tight. Other colloids possessing the same property have been proposed and tried. In the first stages of the development of dope, however, shrinkage was not considered. The fabric was treated merely to render it waterproof. The first airplanes constructed were covered with cotton fabric stretched as tightly as possible over the winds, fuselage, etc., and flying was possible only in fine weather. The necessity of an airplane which would fly under all weather conditions at once became apparent. Then followed experiments with rubberized fabrics, fabrics treated with glue rendered insoluble by formaldehyde or bichromate, fabrics treated with drying and nondrying oils, shellac, casein, etc. It was found that fabrics treated as above lost their tension in damp weather, and the oil from the motor penetrated the proofing material and weakened the fabric. For the most part the film of material lacked durability. Cellulose nitrate lacquers, however were found to be more satisfactory under varying weather conditions, added less weight to the planes, and were easily applied. On the other hand, they were highly inflammable, and oil from the motor penetrated the film of cellulose nitrate, causing the tension of the fabric to be relaxed.

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

    NASA Astrophysics Data System (ADS)

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

    2001-03-01

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

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

    Code of Federal Regulations, 2013 CFR

    2013-07-01

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

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

    Code of Federal Regulations, 2012 CFR

    2012-07-01

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

  6. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

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

  7. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

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

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

    Code of Federal Regulations, 2013 CFR

    2013-07-01

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

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

    Code of Federal Regulations, 2012 CFR

    2012-07-01

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

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

    Code of Federal Regulations, 2014 CFR

    2014-07-01

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

  11. 40 CFR 721.4660 - Alcohol, alkali metal salt.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

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

  12. 40 CFR 721.4660 - Alcohol, alkali metal salt.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

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

  13. 40 CFR 721.5278 - Substituted naphthalenesulfonic acid, alkali salt.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., alkali salt. 721.5278 Section 721.5278 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.5278 Substituted naphthalenesulfonic acid, alkali salt. (a) Chemical... as a substituted naphthalenesulfonic acid, alkali salt (PMN P-95-85) is subject to reporting...

  14. 40 CFR 721.8900 - Substituted halogenated pyridinol, alkali salt.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., alkali salt. 721.8900 Section 721.8900 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.8900 Substituted halogenated pyridinol, alkali salt. (a) Chemical... as substituted halogenated pyridinols, alkali salts (PMNs P-88-1271 and P-88-1272) are subject...

  15. 40 CFR 721.5278 - Substituted naphthalenesulfonic acid, alkali salt.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ..., alkali salt. 721.5278 Section 721.5278 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.5278 Substituted naphthalenesulfonic acid, alkali salt. (a) Chemical... as a substituted naphthalenesulfonic acid, alkali salt (PMN P-95-85) is subject to reporting...

  16. 40 CFR 721.8900 - Substituted halogenated pyridinol, alkali salt.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., alkali salt. 721.8900 Section 721.8900 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.8900 Substituted halogenated pyridinol, alkali salt. (a) Chemical... as substituted halogenated pyridinols, alkali salts (PMNs P-88-1271 and P-88-1272) are subject...

  17. 40 CFR 721.5278 - Substituted naphthalenesulfonic acid, alkali salt.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., alkali salt. 721.5278 Section 721.5278 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.5278 Substituted naphthalenesulfonic acid, alkali salt. (a) Chemical... as a substituted naphthalenesulfonic acid, alkali salt (PMN P-95-85) is subject to reporting...

  18. 40 CFR 721.5278 - Substituted naphthalenesulfonic acid, alkali salt.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ..., alkali salt. 721.5278 Section 721.5278 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.5278 Substituted naphthalenesulfonic acid, alkali salt. (a) Chemical... as a substituted naphthalenesulfonic acid, alkali salt (PMN P-95-85) is subject to reporting...

  19. 40 CFR 721.5278 - Substituted naphthalenesulfonic acid, alkali salt.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ..., alkali salt. 721.5278 Section 721.5278 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.5278 Substituted naphthalenesulfonic acid, alkali salt. (a) Chemical... as a substituted naphthalenesulfonic acid, alkali salt (PMN P-95-85) is subject to reporting...

  20. Structural Characterization of Methanol Substituted Lanthanum Halides

    PubMed Central

    Boyle, Timothy J.; Ottley, Leigh Anna M.; Alam, Todd M.; Rodriguez, Mark A.; Yang, Pin; Mcintyre, Sarah K.

    2010-01-01

    The first study into the alcohol solvation of lanthanum halide [LaX3] derivatives as a means to lower the processing temperature for the production of the LaBr3 scintillators was undertaken using methanol (MeOH). Initially the de-hydration of {[La(µ-Br)(H2O)7](Br)2}2 (1) was investigated through the simple room temperature dissolution of 1 in MeOH. The mixed solvate monomeric [La(H2O)7(MeOH)2](Br)3 (2) compound was isolated where the La metal center retains its original 9-coordination through the binding of two additional MeOH solvents but necessitates the transfer of the innersphere Br to the outersphere. In an attempt to in situ dry the reaction mixture of 1 in MeOH over CaH2, crystals of [Ca(MeOH)6](Br)2 (3) were isolated. Compound 1 dissolved in MeOH at reflux temperatures led to the isolation of an unusual arrangement identified as the salt derivative {[LaBr2.75•5.25(MeOH)]+0.25 [LaBr3.25•4.75(MeOH)]−0.25} (4). The fully substituted species was ultimately isolated through the dissolution of dried LaBr3 in MeOH forming the 8-coordinated [LaBr3(MeOH)5] (5) complex. It was determined that the concentration of the crystallization solution directed the structure isolated (4 concentrated; 5 dilute) The other LaX3 derivatives were isolated as [(MeOH)4(Cl)2La(µ-Cl)]2 (6) and [La(MeOH)9](I)3•MeOH (7). Beryllium Dome XRD analysis indicated that the bulk material for 5 appear to have multiple solvated species, 6 is consistent with the single crystal, and 7 was too broad to elucidate structural aspects. Multinuclear NMR (139La) indicated that these compounds do not retain their structure in MeOD. TGA/DTA data revealed that the de-solvation temperatures of the MeOH derivatives 4 – 6 were slightly higher in comparison to their hydrated counterparts. PMID:20514349

  1. Application of lanthanum halide scintillators and low-resolution dense plastics for modern MC&A needs.

    SciTech Connect

    Chung, K.; Belian, A. P.; McKigney E. A.; Russo, P. A.

    2004-01-01

    Recent developments in lanthanum halide scintillators and low-resolution dense plastics give breadth to gamma-ray methods of nuclear material detection suitable for modern MC and A needs. Demanding goals for modernization of MC and A cover both portable and continuous on-line measurement applications that are quantitative for inventory/verification, and that serve those quantitative measurement needs plant-wide. Improved performance (sensitivity and reoslution) is important for portable applications in which a single detector must measure many types of materials. Budget is a major issue for continuous inventory measurements with hundreds or even thousands of detectors placed throughout a facility. Experimentally proven resolution of under 4% for 662 keV {sup 137}Cs gamma rays measured with large cerium-doped LaCl{sub 3} (lanthanum chloride) crystals set a new performance standard for versatile, efficient portable applications comparable in price to NaI(Tl), which has been dominant for decades. While the relatively high cost of crystals remains an obstacle for the application of very large numbers of lanthanum halide scintillators as distributed networked detectors, scintillators made from high-density plastic offer a different type of solution for these gamma-ray measurements. Compared to lanthanum halide crystals they are inexpensive and can be larger in size. Despite lower resolution than NaI(Tl), a quantitative interpretation of the photopeak response of the low-cost dense plastic detectors can be tailored to the unique mechanical and spectral properties of different materials at each of hundreds of fixed on-line locations in a plant. This paper describes the properties and presents experimental results for the two new spectrometer types that, together, bracket NaI(Tl) detectors in both performance and cost, fulfilling modern demands for portable and continuous on-line accountability of uranium and plutonium.

  2. Computational studies of solid-state alkali conduction in rechargeable alkali-ion batteries

    DOE PAGESBeta

    Deng, Zhi; Mo, Yifei; Ong, Shyue Ping

    2016-03-25

    The facile conduction of alkali ions in a crystal host is of crucial importance in rechargeable alkali-ion batteries, the dominant form of energy storage today. In this review, we provide a comprehensive survey of computational approaches to study solid-state alkali diffusion. We demonstrate how these methods have provided useful insights into the design of materials that form the main components of a rechargeable alkali-ion battery, namely the electrodes, superionic conductor solid electrolytes and interfaces. We will also provide a perspective on future challenges and directions. Here, the scope of this review includes the monovalent lithium- and sodium-ion chemistries that aremore » currently of the most commercial interest.« less

  3. Alkali resistant optical coatings for alkali lasers and methods of production thereof

    DOEpatents

    Soules, Thomas F; Beach, Raymond J; Mitchell, Scott C

    2014-11-18

    In one embodiment, a multilayer dielectric coating for use in an alkali laser includes two or more alternating layers of high and low refractive index materials, wherein an innermost layer includes a thicker, >500 nm, and dense, >97% of theoretical, layer of at least one of: alumina, zirconia, and hafnia for protecting subsequent layers of the two or more alternating layers of high and low index dielectric materials from alkali attack. In another embodiment, a method for forming an alkali resistant coating includes forming a first oxide material above a substrate and forming a second oxide material above the first oxide material to form a multilayer dielectric coating, wherein the second oxide material is on a side of the multilayer dielectric coating for contacting an alkali.

  4. Terahertz radiation in alkali vapor plasmas

    SciTech Connect

    Sun, Xuan; Zhang, X.-C.

    2014-05-12

    By taking advantage of low ionization potentials of alkali atoms, we demonstrate terahertz wave generation from cesium and rubidium vapor plasmas with an amplitude nearly one order of magnitude larger than that from nitrogen gas at low pressure (0.02–0.5 Torr). The observed phenomena are explained by the numerical modeling based upon electron tunneling ionization.

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

    PubMed Central

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

    2014-01-01

    A novel extracellular thermo-alkali-stable laccase from Bacillus tequilensis SN4 (SN4LAC) was purified to homogeneity. The laccase was a monomeric protein of molecular weight 32 KDa. UV-visible spectrum and peptide mass fingerprinting results showed that SN4LAC is a multicopper oxidase. Laccase was active in broad range of phenolic and non-phenolic substrates. Catalytic efficiency (kcat/Km) showed that 2, 6-dimethoxyphenol was most efficiently oxidized by the enzyme. The enzyme was inhibited by conventional inhibitors of laccase like sodium azide, cysteine, dithiothreitol and β-mercaptoethanol. SN4LAC was found to be highly thermostable, having temperature optimum at 85°C and could retain more than 80% activity at 70°C for 24 h. The optimum pH of activity for 2, 6-dimethoxyphenol, 2, 2′-azino bis[3-ethylbenzthiazoline-6-sulfonate], syringaldazine and guaiacol was 8.0, 5.5, 6.5 and 8.0 respectively. Enzyme was alkali-stable as it retained more than 75% activity at pH 9.0 for 24 h. Activity of the enzyme was significantly enhanced by Cu2+, Co2+, SDS and CTAB, while it was stable in the presence of halides, most of the other metal ions and surfactants. The extracellular nature and stability of SN4LAC in extreme conditions such as high temperature, pH, heavy metals, halides and detergents makes it a highly suitable candidate for biotechnological and industrial applications. PMID:24871763

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

    PubMed

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

    2014-01-01

    A novel extracellular thermo-alkali-stable laccase from Bacillus tequilensis SN4 (SN4LAC) was purified to homogeneity. The laccase was a monomeric protein of molecular weight 32 KDa. UV-visible spectrum and peptide mass fingerprinting results showed that SN4LAC is a multicopper oxidase. Laccase was active in broad range of phenolic and non-phenolic substrates. Catalytic efficiency (kcat/Km) showed that 2, 6-dimethoxyphenol was most efficiently oxidized by the enzyme. The enzyme was inhibited by conventional inhibitors of laccase like sodium azide, cysteine, dithiothreitol and β-mercaptoethanol. SN4LAC was found to be highly thermostable, having temperature optimum at 85°C and could retain more than 80% activity at 70°C for 24 h. The optimum pH of activity for 2, 6-dimethoxyphenol, 2, 2'-azino bis[3-ethylbenzthiazoline-6-sulfonate], syringaldazine and guaiacol was 8.0, 5.5, 6.5 and 8.0 respectively. Enzyme was alkali-stable as it retained more than 75% activity at pH 9.0 for 24 h. Activity of the enzyme was significantly enhanced by Cu2+, Co2+, SDS and CTAB, while it was stable in the presence of halides, most of the other metal ions and surfactants. The extracellular nature and stability of SN4LAC in extreme conditions such as high temperature, pH, heavy metals, halides and detergents makes it a highly suitable candidate for biotechnological and industrial applications. PMID:24871763

  7. Hyaline membrane disease, alkali, and intraventricular haemorrhage.

    PubMed Central

    Wigglesworth, J S; Keith, I H; Girling, D J; Slade, S A

    1976-01-01

    The relation between intraventricular haemorrhage (IVH) and hyaline membrane disease (HMD) was studied in singletons that came to necropsy at Hammersmith Hospital over the years 1966-73. The incidence of IVH in singleton live births was 3-22/1000 and of HMD 4-44/1000. Although the high figures were partily due to the large number of low birthweight infants born at this hospital, the incidence of IVH in babies weighing 1001-1500 g was three times as great as that reported in the 1658 British Perinatal Mortality Survey. Most IVH deaths were in babies with HMD, but the higher frequency of IVH was not associated with any prolongation of survival time of babies who died with HMD as compared with the 1958 survey. IVH was seen frequently at gestations of up to 36 weeks in babies with HMD but was rare above 30 weeks' gestation in babies without HMD. This indicated that factors associated with HMD must cause most cases of IVH seen at gestations above 30 weeks. Comparison of clinical details in infants with HMD who died with or without IVH (at gestations of 30-37 weeks) showed no significant differences between the groups other than a high incidence of fits and greater use of alkali therapy in the babies with IVH. During the 12 hours when most alkali therapy was given, babies dying with IVD received a mean total alkali dosage of 10-21 mmol/kg and those dying without IVH 6-34 mmol/kg (P less than 0-001).There was no difference in severity of hypoxia or of metabolic acidosis between the 2 groups. Babies who died with HMD and germinal layer haemorrhage (GLH) without IVH had received significantly more alkali than those who died with HMD alone, whereas survivors of severe respiratory distress syndrome had received lower alkali doses than other groups. It is suggested that the greatly increased death rate from IVH in babies with HMD indicates some alteration of management of HMD (since 1958) as a causative factor. Liberal use of hypertonic alkali solutions is the common factor

  8. 40 CFR 721.10698 - Polyfluorinated alkyl halide (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Polyfluorinated alkyl halide (generic). 721.10698 Section 721.10698 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances §...

  9. Kinetic Studies of the Solvolysis of Two Organic Halides

    ERIC Educational Resources Information Center

    Duncan, J. A.; Pasto, D. J.

    1975-01-01

    Describes an undergraduate organic chemistry laboratory experiment which utilizes the solvolysis of organic halides to demonstrate first and second order reaction kinetics. The experiment also investigates the effect of a change of solvent polarity on reaction rate, common-ion and noncommon-ion salt effects, and the activation parameters of a…

  10. Method for calcining nuclear waste solutions containing zirconium and halides

    DOEpatents

    Newby, Billie J.

    1979-01-01

    A reduction in the quantity of gelatinous solids which are formed in aqueous zirconium-fluoride nuclear reprocessing waste solutions by calcium nitrate added to suppress halide volatility during calcination of the solution while further suppressing chloride volatility is achieved by increasing the aluminum to fluoride mole ratio in the waste solution prior to adding the calcium nitrate.

  11. Methyl halide emission estimates from domestic biomass burning in Africa

    NASA Astrophysics Data System (ADS)

    Mead, M. I.; Khan, M. A. H.; White, I. R.; Nickless, G.; Shallcross, D. E.

    Inventories of methyl halide emissions from domestic burning of biomass in Africa, from 1950 to the present day and projected to 2030, have been constructed. By combining emission factors from Andreae and Merlet [2001. Emission of trace gases and aerosols from biomass burning. Global Biogeochemical Cycles 15, 955-966], the biomass burning estimates from Yevich and Logan [2003. An assessment of biofuel use and burning of agricultural waste in the developing world. Global Biogeochemical Cycles 17(4), 1095, doi:10.1029/2002GB001952] and the population data from the UN population division, the emission of methyl halides from domestic biomass usage in Africa has been estimated. Data from this study suggest that methyl halide emissions from domestic biomass burning have increased by a factor of 4-5 from 1950 to 2005 and based on the expected population growth could double over the next 25 years. This estimated change has a non-negligible impact on the atmospheric budgets of methyl halides.

  12. Students' Understanding of Alkyl Halide Reactions in Undergraduate Organic Chemistry

    ERIC Educational Resources Information Center

    Cruz-Ramirez de Arellano, Daniel

    2013-01-01

    Organic chemistry is an essential subject for many undergraduate students completing degrees in science, engineering, and pre-professional programs. However, students often struggle with the concepts and skills required to successfully solve organic chemistry exercises. Since alkyl halides are traditionally the first functional group that is…

  13. On the Boiling Points of the Alkyl Halides.

    ERIC Educational Resources Information Center

    Correia, John

    1988-01-01

    Discusses the variety of explanations in organic chemistry textbooks of a physical property of organic compounds. Focuses on those concepts explaining attractive forces between molecules. Concludes that induction interactions play a major role in alkyl halides and other polar organic molecules and should be given wider exposure in chemistry texts.…

  14. Semiempirical and DFT Investigations of the Dissociation of Alkyl Halides

    ERIC Educational Resources Information Center

    Waas, Jack R.

    2006-01-01

    Enthalpy changes corresponding to the gas phase heats of dissociation of 12 organic halides were calculated using two semiempirical methods, the Hartree-Fock method, and two DFT methods. These calculated values were compared to experimental values where possible. All five methods agreed generally with the expected empirically known trends in the…

  15. CO2 electrochemical reduction via adsorbed halide anions

    NASA Astrophysics Data System (ADS)

    Ogura, Kotaro; Salazar-Villalpando, Maria D.

    2011-01-01

    The electrochemical reduction of CO2 was studied utilizing halide ions as electrolytes, specifically, aqueous solutions of KCl, KBr, KI. Electrochemical experiments were carried out in a laboratory-made, divided H-type cell. The working electrode was a copper mesh, while the counter and reference electrodes were a Pt wire and an Ag/AgCl electrode, respectively. The results of our work suggest a reaction mechanism for the electrochemical reduction of CO2 where the presence of Cu-X as the catalytic layer facilitates the electron transfer from the electrode to CO2. Electron-transfer to CO2 may occur via the X- ad(Br-, Cl-, I-)-C bond, which is formed by the electron flow from the specifically adsorbed halide anion to the vacant orbital of CO2. The stronger the adsorption of the halide anion to the electrode, the more strongly CO2 is restrained, resulting in higher CO2 reduction current. Furthermore, it is suggested that specifically adsorbed halide anions could suppress the adsorption of protons; leading to a higher hydrogen overvoltage. These effects may synergistically mitigate the over potential necessary for CO2 reduction, and thus increase the rate of electrochemical CO2 reduction.

  16. Structure of lithium-doped polyacetylene

    NASA Astrophysics Data System (ADS)

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

    1989-12-01

    A trigonal structure with three polymer chains per lithium column is proposed for lithium-doped polyacetylene. A calculation of the x-ray diffraction profile, using the unit-cell dimension and the lithium concentration as the only variables, is in good agreement with the observed data. The proposed structure optimizes the electrostatic interactions by maximizing both the Li+-Li+ separations and the coordination of negatively charged carbons and positively charged lithiums. Unlike the tetragonal lattice found in polyacetylene complexed with larger alkali-metal ions (K+, Rb+, and Cs+), the trigonal structure permits the undoped and the doped phases to coexist without any significant lattice mismatch at the boundary between the two phases. While the chain axis expands by ~1% upon doping with lithium, the projected area per chain remains essentially unchanged.

  17. Physics and chemistry of alkali-silica reactions

    SciTech Connect

    Diamond, S.; Barneyback, R.S. Jr.; Struble, L.J.

    1981-01-01

    The philosophy underlying recent research on alkali-silica reactions is reviewed and illustrations of recent results are provided. It has been possible to follow the kinetics of the chemical reaction between dissolved alkalis and opal in mortars by monitoring the rate at which alkalis are removed from the pore solutions of reacting mortars. Studies of the expansion behavior of synthetic alkali silica gels under controlled conditions were carried out and show no obvious correlation to chemical composition. The alkali reaction in mortars was found to produce changes in the appearance of opal grains documentable by the use of a scanning electron microscope.

  18. Calcium-Alkali Syndrome in the Modern Era

    PubMed Central

    Patel, Ami M.; Adeseun, Gbemisola A.; Goldfarb, Stanley

    2013-01-01

    The ingestion of calcium, along with alkali, results in a well-described triad of hypercalcemia, metabolic alkalosis, and renal insufficiency. Over time, the epidemiology and root cause of the syndrome have shifted, such that the disorder, originally called the milk-alkali syndrome, is now better described as the calcium-alkali syndrome. The calcium-alkali syndrome is an important cause of morbidity that may be on the rise, an unintended consequence of shifts in calcium and vitamin D intake in segments of the population. We review the pathophysiology of the calcium-alkali syndrome. PMID:24288027

  19. Alkali metal recovery from carbonaceous material conversion process

    DOEpatents

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

    1980-01-01

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

  20. Alkali element background reduction in laser ICP-MS

    NASA Astrophysics Data System (ADS)

    Magee, C. W., Jr.; Norris, C. A.

    2014-11-01

    Alkali backgrounds in laser ablation ICP-MS analyses can be enhanced by electron-induced ionization of alkali contamination on the skimmer cone, reducing effective detection limits for these elements. Traditionally, this problem is addressed by isolating analyses of high alkali materials onto a designated cone set, or by operating the ICP-MS in a "soft extraction" mode, which reduces the energy of electrons repelled into the potentially contaminated sampling cone by the extraction field. Here we present a novel approach, where we replace the traditional alkali glass tuning standards with synthetic low-alkali glass reference materials. Using this vitreous tuning solution, we find that this approach reduces the amount of alkali contamination produced, halving backgrounds for the heavy alkali elements without any change to analytical procedures. Using segregated cones is still the most effective method for reducing lithium backgrounds, but since the procedures are complimentary both can easily be applied to the routine operations of an analytical lab.

  1. Alkali element background reduction in laser ICP-MS

    NASA Astrophysics Data System (ADS)

    Magee, C. W., Jr.; Norris, C. A.

    2015-03-01

    Alkali backgrounds in laser ablation ICP-MS analyses can be enhanced by electron-induced ionisation of alkali contamination on the skimmer cone, reducing effective detection limits for these elements. Traditionally, this problem is addressed by isolating analyses of high-alkali materials onto a designated cone set, or by operating the ICP-MS in a "soft extraction" mode, which reduces the energy of electrons repelled into the potentially contaminated sampling cone by the extraction field. Here we present a novel approach, where we replace the traditional alkali glass tuning standards with synthetic low-alkali glass reference materials. Using this vitreous tuning solution, we find that this approach reduces the amount of alkali contamination produced, halving backgrounds for the heavy alkali elements without any change to analytical procedures. Using segregated cones is still the most effective method for reducing lithium backgrounds, but since the procedures are complimentary, both can easily be applied to the routine operations of an analytical lab.

  2. Developments in alkali-metal atomic magnetometry

    NASA Astrophysics Data System (ADS)

    Seltzer, Scott Jeffrey

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

  3. Effect of alkali lignins with different molecular weights from alkali pretreated rice straw hydrolyzate on enzymatic hydrolysis.

    PubMed

    Li, Yun; Qi, Benkun; Luo, Jianquan; Wan, Yinhua

    2016-01-01

    This study investigated the effect of alkali lignins with different molecular weights on enzymatic hydrolysis of lignocellulose. Different alkali lignins fractions, which were obtained from cascade ultrafiltration, were added into the dilute acid pretreated (DAP) and alkali pretreated (AP) rice straws respectively during enzymatic hydrolysis. The results showed that the addition of alkali lignins enhanced the hydrolysis and the enhancement for hydrolysis increased with increasing molecular weights of alkali lignins, with maximum enhancement being 28.69% for DAP and 20.05% for AP, respectively. The enhancement was partly attributed to the improved cellulase activity, and filter paper activity increased by 18.03% when adding lignin with highest molecular weight. It was found that the enhancement of enzymatic hydrolysis was correlated with the adsorption affinity of cellulase on alkali lignins, and the difference in surface charge and hydrophobicity of alkali lignins were responsible for the difference in affinity between cellulase and lignins. PMID:26496216

  4. Rare-Earth Tri-Halide Methanol-Adduct Single-Crystal Scintillators for Gamma Ray and Neutron Detection - 8/17/09

    SciTech Connect

    Boatner, Lynn A; Wisniewski, D.; Neal, John S; Bell, Zane W; Ramey, Joanne Oxendine; Kolopus, James A; Chakoumakos, Bryan C; Custelcean, Radu; Wisniewska, Monika; Peña, K. E.

    2009-01-01

    Cerium activated rare-earth tri- halides represent a well-known family of high performance inorganic rare-earth scintillators - including the high-light-yield, high-energy-resolution scintillator, cerium-doped lanthanum tribromide. These hygroscopic inorganic rare-earth halides are currently grown as single crystals from the melt - either by the Bridgman or Czochralski techniques slow and expensive processes that are frequently characterized by severe cracking of the material due to anisotropic thermal stresses and cleavage effects. We have recently discovered a new family of cerium-activated rare-earth metal organic scintillators consisting of tri-halide methanol adducts of cerium and lanthanum namely CeCl3(CH3OH)4 and LaBr3(CH3OH)4:Ce. These methanol-adduct scintillator materials can be grown near room temperature from a methanol solution, and their high solubility is consistent with the application of the rapid solution growth methods that are currently used to grow very large single crystals of potassium dihydrogen phosphate. The structures of these new rare-earth metal-organic scintillating compounds were determined by single crystal x-ray refinements, and their scintillation response to both gamma rays and neutrons, as presented here, was characterized using different excitation sources. Tri-halide methanol-adduct crystals activated with trivalent cerium apparently represent the initial example of a solution-grown rare-earth metal-organic molecular scintillator that is applicable to gamma ray, x-ray, and fast neutron detection.

  5. Spectroscopic effects of disorder and vibrational localization in mixed-halide metal-halide chain solids

    SciTech Connect

    Love, S.P.; Scott, B.; Worl, L.A.; Huckett, S.C.; Saxena, A.; Huang, X.Z.; Bishop, A.R.; Swanson, B.I.

    1993-02-01

    Resonance Raman techniques, together with lattice-dynamics and Peierls-Hubbard modelling, are used to explore the electronic and vibrational dynamics of the quasi-one-dimensional metal-halogen chain solids [Pt(en){sub 2}][R(en){sub 2}X{sub 2}](ClO{sub 4}){sub 4}, (en = C{sub 2}H{sub 8}N{sub 2} and X=Cl, Br), abbreviated ``PLX.`` The mixed-halide materials PtCl{sub 1-x}Br{sub x} and PtCl{sub 1-x}I{sub x} consist of long mixed chains with heterojunctions between segments of the two constituent materials. Thus, in addition to providing mesoscale modulation of the chain electronic states, they serve as prototypes for elucidating the properties to be expected for macroscopic heterojunctions of these highly nonlinear materials. Once a detailed understanding of the various local vibrational modes occurring in these disordered solids is developed, the electronic structure of the chain segments and junctions can be probed by tuning the Raman excitation through their various electronic resonances.

  6. Matrix isolation infrared spectra of hydrogen halide and halogen complexes with nitrosyl halides

    NASA Technical Reports Server (NTRS)

    Allamandola, Louis J.; Lucas, Donald; Pimentel, George C.

    1982-01-01

    Matrix isolation infrared spectra of nitrosyl halide (XNO) complexes with HX and X2 (X = Cl, Br) are presented. The relative frequency shifts of the HX mode are modest (ClNO H-Cl, delta-nu/nu = -0.045; BrNO H-Br, delta-nu/nu = -0.026), indicating weak hydrogen bonds 1-3 kcal/mol. These shifts are accompanied by significant shifts to higher frequencies in the XN-O stretching mode (CIN-O HCl, delta-nu/nu = +0.016; BrN-O HBr, delta-nu/nu = +0.011). Similar shifts were observed for the XN-O X2 complexes (ClN-O Cl2, delta-nu/nu = +0.009; BrN-O-Br2, delta-nu/nu = +0.013). In all four complexes, the X-NO stretching mode relative shift is opposite in sign and about 1.6 times that of the NO stretching mode. These four complexes are considered to be similar in structure and charge distribution. The XN-O frequency shift suggests that complex formation is accompanied by charge withdrawal from the NO bond ranging from about .04 to .07 electron charges. The HX and X2 molecules act as electron acceptors, drawing electrons out of the antibonding orbital of NO and strengthening the XN-O bond. The implications of the pattern of vibrational shifts concerning the structure of the complexes are discussed.

  7. Removal of Retired Alkali Metal Test Systems

    SciTech Connect

    BREHM, W.F.

    2003-01-01

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

  8. Removal of Retired Alkali Metal Test Systems

    SciTech Connect

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

    2003-02-26

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

  9. Geopolymers and Related Alkali-Activated Materials

    NASA Astrophysics Data System (ADS)

    Provis, John L.; Bernal, Susan A.

    2014-07-01

    The development of new, sustainable, low-CO2 construction materials is essential if the global construction industry is to reduce the environmental footprint of its activities, which is incurred particularly through the production of Portland cement. One type of non-Portland cement that is attracting particular attention is based on alkali-aluminosilicate chemistry, including the class of binders that have become known as geopolymers. These materials offer technical properties comparable to those of Portland cement, but with a much lower CO2 footprint and with the potential for performance advantages over traditional cements in certain niche applications. This review discusses the synthesis of alkali-activated binders from blast furnace slag, calcined clay (metakaolin), and fly ash, including analysis of the chemical reaction mechanisms and binder phase assemblages that control the early-age and hardened properties of these materials, in particular initial setting and long-term durability. Perspectives for future research developments are also explored.

  10. Quantum magnetism of alkali Rydberg atoms

    NASA Astrophysics Data System (ADS)

    Malinovskaya, Svetlana; Liu, Gengyuan

    2016-05-01

    We discuss a method to control dynamics in many-body spin states of 87Rb Rydberg atoms. The method permits excitation of cold gases and form ordered structures of alkali atoms. It makes use of a two-photon excitation scheme with circularly polarized and linearly chirped pulses. The method aims for controlled quantum state preparation in large ensembles. It is actual for experiments studding the spin hopping dynamics and realization of quantum random walks.

  11. Alkali Metal Heat Pipe Life Issues

    NASA Technical Reports Server (NTRS)

    Reid, Robert S.

    2004-01-01

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

  12. Alkali metal protective garment and composite material

    SciTech Connect

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

    1980-09-16

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

  13. Alkali metal protective garment and composite material

    SciTech Connect

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

    1980-01-01

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

  14. Study of superconducting state parameters of alkali alkali binary alloys by a pseudopotential

    NASA Astrophysics Data System (ADS)

    Vora, Aditya M.

    2006-12-01

    A detailed study of the superconducting state parameters (SSP) viz. electron-phonon coupling strength λ, Coulomb pseudopotential μ∗, transition temperature TC, isotope effect exponent α and effective interaction strength N OV of ten alkali-alkali binary alloys i.e. Li 1- xNa x, Li 1- xK x, Li 1- xRb x, Li 1- xCs x, Na 1- xK x, Na 1- xRb x, Na 1- xCs x, K 1- xRb x, K 1- xCs x and Rb 1- xCs x are made within the framework of the model potential formalism and employing the pseudo-alloy-atom (PAA) model for the first time. We use the Ashcroft’s empty core (EMC) model potential for evaluating the superconducting properties of alkali alloys. Five different forms of local field correction functions viz. Hartree (H), Taylor (T), Ichimaru-Utsumi (IU), Farid et al. (F) and Sarkar et al. (S) are used to incorporate the exchange and correlation effects. A considerable influence of various exchange and correlation functions on λ and μ∗ is found from the present study. Reasonable agreement with the theoretical values of the SSP of pure components is found (corresponding to the concentration x = 0 or 1). It is also concluded that nature of the SSP strongly depends on the value of the atomic volume Ω0 of alkali-alkali binary alloys.

  15. Ion Pairing in Alkali Nitrate Electrolyte Solutions.

    PubMed

    Xie, Wen Jun; Zhang, Zhen; Gao, Yi Qin

    2016-03-10

    In this study, we investigate the thermodynamics of alkali nitrate salt solutions, especially the formation of contact ion pairs between alkali cation and nitrate anion. The ion-pairing propensity shows an order of LiNO3 < NaNO3 < KNO3. Such results explain the salt activity coefficients and suggest that the empirical "law of matching water affinity" is followed by these alkali nitrate salt solutions. The spatial patterns of contact ion pairs are different in the three salt solutions studied here: Li(+) forms the contact ion pair with only one oxygen of the nitrate while Na(+) and K(+) can also be shared by two oxygens of the nitrate. In reproducing the salt activity coefficient using Kirkwood-Buff theory, we find that it is essential to include electronic polarization for Li(+) which has a high charge density. The electronic continuum correction for nonpolarizable force field significantly improves the agreement between the calculated activity coefficients and their experimental values. This approach also improves the performance of the force field on salt solubility. From these two aspects, this study suggests that electronic continuum correction can be a promising approach to force-field development for ions with high charge densities. PMID:26901167

  16. Waveshifting fiber readout of lanthanum halide scintillators

    NASA Astrophysics Data System (ADS)

    Case, G. L.; Cherry, M. L.; Stacy, J. G.

    2006-07-01

    Newly developed high-light-yield inorganic scintillators coupled to waveshifting optical fibers provide the capability of efficient X-ray detection and millimeter scale position resolution suitable for high-energy cosmic ray instruments, hard X-ray/gamma ray astronomy telescopes and applications to national security. The CASTER design for NASA's proposed Black Hole Finder Probe mission, in particular, calls for a 6 8 m2 hard X-ray coded aperture imaging telescope operating in the 20 600 keV energy band, putting significant constraints on cost and readout complexity. The development of new inorganic scintillator materials (e.g., cerium-doped LaBr3 and LaCl3) provides improved energy resolution and timing performance that is well suited to the requirements for national security and astrophysics applications. LaBr3 or LaCl3 detector arrays coupled with waveshifting fiber optic readout represent a significant advance in the performance capabilities of scintillator-based gamma cameras and provide the potential for a feasible approach to affordable, large area, extremely sensitive detectors. We describe some of the applications and present laboratory test results demonstrating the expected scintillator performance.

  17. Methods and Mechanisms for Cross-Electrophile Coupling of Csp(2) Halides with Alkyl Electrophiles.

    PubMed

    Weix, Daniel J

    2015-06-16

    Cross-electrophile coupling, the cross-coupling of two different electrophiles, avoids the need for preformed carbon nucleophiles, but development of general methods has lagged behind cross-coupling and C-H functionalization. A central reason for this slow development is the challenge of selectively coupling two substrates that are alike in reactivity. This Account describes the discovery of generally cross-selective reactions of aryl halides and acyl halides with alkyl halides, the mechanistic studies that illuminated the underlying principles of these reactions, and the use of these fundamental principles in the rational design of new cross-electrophile coupling reactions. Although the coupling of two different electrophiles under reducing conditions often leads primarily to symmetric dimers, the subtle differences in reactivity of aryl halides and alkyl halides with nickel catalysts allowed for generally cross-selective coupling reactions. These conditions could also be extended to the coupling of acyl halides with alkyl halides. These reactions are exceptionally functional group tolerant and can be assembled on the benchtop. A combination of stoichiometric and catalytic studies on the mechanism of these reactions revealed an unusual radical-chain mechanism and suggests that selectivity arises from (1) the preference of nickel(0) for oxidative addition to aryl halides and acyl halides over alkyl halides and (2) the greater propensity of alkyl halides to form free radicals. Bipyridine-ligated arylnickel intermediates react with alkyl radicals to efficiently form, after reductive elimination, new C-C bonds. Finally, the resulting nickel(I) species is proposed to regenerate an alkyl radical to carry the chain. Examples of new reactions designed using these principles include carbonylative coupling of aryl halides with alkyl halides to form ketones, arylation of epoxides to form β-aryl alcohols, and coupling of benzyl sulfonate esters with aryl halides to form

  18. Methods and Mechanisms for Cross-Electrophile Coupling of Csp2 Halides with Alkyl Electrophiles

    PubMed Central

    2016-01-01

    Conspectus Cross-electrophile coupling, the cross-coupling of two different electrophiles, avoids the need for preformed carbon nucleophiles, but development of general methods has lagged behind cross-coupling and C–H functionalization. A central reason for this slow development is the challenge of selectively coupling two substrates that are alike in reactivity. This Account describes the discovery of generally cross-selective reactions of aryl halides and acyl halides with alkyl halides, the mechanistic studies that illuminated the underlying principles of these reactions, and the use of these fundamental principles in the rational design of new cross-electrophile coupling reactions. Although the coupling of two different electrophiles under reducing conditions often leads primarily to symmetric dimers, the subtle differences in reactivity of aryl halides and alkyl halides with nickel catalysts allowed for generally cross-selective coupling reactions. These conditions could also be extended to the coupling of acyl halides with alkyl halides. These reactions are exceptionally functional group tolerant and can be assembled on the benchtop. A combination of stoichiometric and catalytic studies on the mechanism of these reactions revealed an unusual radical-chain mechanism and suggests that selectivity arises from (1) the preference of nickel(0) for oxidative addition to aryl halides and acyl halides over alkyl halides and (2) the greater propensity of alkyl halides to form free radicals. Bipyridine-ligated arylnickel intermediates react with alkyl radicals to efficiently form, after reductive elimination, new C–C bonds. Finally, the resulting nickel(I) species is proposed to regenerate an alkyl radical to carry the chain. Examples of new reactions designed using these principles include carbonylative coupling of aryl halides with alkyl halides to form ketones, arylation of epoxides to form β-aryl alcohols, and coupling of benzyl sulfonate esters with aryl

  19. Efficient hole-blocking layer-free planar halide perovskite thin-film solar cells

    NASA Astrophysics Data System (ADS)

    Ke, Weijun; Fang, Guojia; Wan, Jiawei; Tao, Hong; Liu, Qin; Xiong, Liangbin; Qin, Pingli; Wang, Jing; Lei, Hongwei; Yang, Guang; Qin, Minchao; Zhao, Xingzhong; Yan, Yanfa

    2015-03-01

    Efficient lead halide perovskite solar cells use hole-blocking layers to help collection of photogenerated electrons and to achieve high open-circuit voltages. Here, we report the realization of efficient perovskite solar cells grown directly on fluorine-doped tin oxide-coated substrates without using any hole-blocking layers. With ultraviolet-ozone treatment of the substrates, a planar Au/hole-transporting material/CH3NH3PbI3-xClx/substrate cell processed by a solution method has achieved a power conversion efficiency of over 14% and an open-circuit voltage of 1.06 V measured under reverse voltage scan. The open-circuit voltage is as high as that of our best reference cell with a TiO2 hole-blocking layer. Besides ultraviolet-ozone treatment, we find that involving Cl in the synthesis is another key for realizing high open-circuit voltage perovskite solar cells without hole-blocking layers. Our results suggest that TiO2 may not be the ultimate interfacial material for achieving high-performance perovskite solar cells.

  20. Efficient hole-blocking layer-free planar halide perovskite thin-film solar cells.

    PubMed

    Ke, Weijun; Fang, Guojia; Wan, Jiawei; Tao, Hong; Liu, Qin; Xiong, Liangbin; Qin, Pingli; Wang, Jing; Lei, Hongwei; Yang, Guang; Qin, Minchao; Zhao, Xingzhong; Yan, Yanfa

    2015-01-01

    Efficient lead halide perovskite solar cells use hole-blocking layers to help collection of photogenerated electrons and to achieve high open-circuit voltages. Here, we report the realization of efficient perovskite solar cells grown directly on fluorine-doped tin oxide-coated substrates without using any hole-blocking layers. With ultraviolet-ozone treatment of the substrates, a planar Au/hole-transporting material/CH₃NH₃PbI₃-xClx/substrate cell processed by a solution method has achieved a power conversion efficiency of over 14% and an open-circuit voltage of 1.06 V measured under reverse voltage scan. The open-circuit voltage is as high as that of our best reference cell with a TiO₂ hole-blocking layer. Besides ultraviolet-ozone treatment, we find that involving Cl in the synthesis is another key for realizing high open-circuit voltage perovskite solar cells without hole-blocking layers. Our results suggest that TiO₂ may not be the ultimate interfacial material for achieving high-performance perovskite solar cells. PMID:25798925

  1. Gaseous NH3 Confers Porous Pt Nanodendrites Assisted by Halides.

    PubMed

    Lu, Shuanglong; Eid, Kamel; Li, Weifeng; Cao, Xueqin; Pan, Yue; Guo, Jun; Wang, Liang; Wang, Hongjing; Gu, Hongwei

    2016-01-01

    Tailoring the morphology of Pt nanocrystals (NCs) is of great concern for their enhancement in catalytic activity and durability. In this article, a novel synthetic strategy is developed to selectively prepare porous dendritic Pt NCs with different structures for oxygen reduction reaction (ORR) assisted by NH3 gas and halides (F(-), Cl(-), Br(-)). The NH3 gas plays critical roles on tuning the morphology. Previously, H2 and CO gas are reported to assist the shape control of metallic nanocrystals. This is the first demonstration that NH3 gas assists the Pt anisotropic growth. The halides also play important role in the synthetic strategy to regulate the formation of Pt NCs. As-made porous dendritic Pt NCs, especially when NH4F is used as a regulating reagent, show superior catalytic activity for ORR compared with commercial Pt/C catalyst and other previously reported Pt-based NCs. PMID:27184228

  2. Gaseous NH3 Confers Porous Pt Nanodendrites Assisted by Halides

    PubMed Central

    Lu, Shuanglong; Eid, Kamel; Li, Weifeng; Cao, Xueqin; Pan, Yue; Guo, Jun; Wang, Liang; Wang, Hongjing; Gu, Hongwei

    2016-01-01

    Tailoring the morphology of Pt nanocrystals (NCs) is of great concern for their enhancement in catalytic activity and durability. In this article, a novel synthetic strategy is developed to selectively prepare porous dendritic Pt NCs with different structures for oxygen reduction reaction (ORR) assisted by NH3 gas and halides (F−, Cl−, Br−). The NH3 gas plays critical roles on tuning the morphology. Previously, H2 and CO gas are reported to assist the shape control of metallic nanocrystals. This is the first demonstration that NH3 gas assists the Pt anisotropic growth. The halides also play important role in the synthetic strategy to regulate the formation of Pt NCs. As-made porous dendritic Pt NCs, especially when NH4F is used as a regulating reagent, show superior catalytic activity for ORR compared with commercial Pt/C catalyst and other previously reported Pt-based NCs. PMID:27184228

  3. Gaseous NH3 Confers Porous Pt Nanodendrites Assisted by Halides

    NASA Astrophysics Data System (ADS)

    Lu, Shuanglong; Eid, Kamel; Li, Weifeng; Cao, Xueqin; Pan, Yue; Guo, Jun; Wang, Liang; Wang, Hongjing; Gu, Hongwei

    2016-05-01

    Tailoring the morphology of Pt nanocrystals (NCs) is of great concern for their enhancement in catalytic activity and durability. In this article, a novel synthetic strategy is developed to selectively prepare porous dendritic Pt NCs with different structures for oxygen reduction reaction (ORR) assisted by NH3 gas and halides (F‑, Cl‑, Br‑). The NH3 gas plays critical roles on tuning the morphology. Previously, H2 and CO gas are reported to assist the shape control of metallic nanocrystals. This is the first demonstration that NH3 gas assists the Pt anisotropic growth. The halides also play important role in the synthetic strategy to regulate the formation of Pt NCs. As-made porous dendritic Pt NCs, especially when NH4F is used as a regulating reagent, show superior catalytic activity for ORR compared with commercial Pt/C catalyst and other previously reported Pt-based NCs.

  4. Large methyl halide emissions from south Texas salt marshes

    NASA Astrophysics Data System (ADS)

    Rhew, R. C.; Whelan, M. E.; Min, D.-H.

    2014-06-01

    Coastal salt marshes are natural sources of methyl chloride (CH3Cl) and methyl bromide (CH3Br) to the atmosphere, but measured emission rates vary widely by geography. Here we report large methyl halide fluxes from subtropical salt marshes of south Texas. Sites with the halophytic plant, Batis maritima, emitted methyl halides at rates that are orders of magnitude greater than sites containing other vascular plants or macroalgae. B. maritima emissions were generally highest at midday; however, diurnal variability was more pronounced for CH3Br than CH3Cl, and surprisingly high nighttime CH3Cl fluxes were observed in July. Seasonal and intra-site variability were large, even taking into account biomass differences. Overall, these subtropical salt marsh sites show much higher emission rates than temperate salt marshes at similar times of the year, supporting the contention that low-latitude salt marshes are significant sources of CH3Cl and CH3Br.

  5. Large methyl halide emissions from south Texas salt marshes

    NASA Astrophysics Data System (ADS)

    Rhew, R. C.; Whelan, M. E.; Min, D.-H.

    2014-11-01

    Coastal salt marshes are natural sources of methyl chloride (CH3Cl) and methyl bromide (CH3Br) to the atmosphere, but measured emission rates vary widely by geography. Here we report large methyl halide fluxes from subtropical salt marshes of south Texas. Sites with the halophytic plant, Batis maritima, emitted methyl halides at rates that are orders of magnitude greater than sites containing other vascular plants or macroalgae. B. maritima emissions were generally highest at midday; however, diurnal variability was more pronounced for CH3Br than CH3Cl, and surprisingly high nighttime CH3Cl fluxes were observed in July. Seasonal and intra-site variability were large, even taking into account biomass differences. Overall, these subtropical salt marsh sites show much higher emission rates than temperate salt marshes at similar times of the year, supporting the contention that low-latitude salt marshes are significant sources of CH3Cl and CH3Br.

  6. Oxidative alkoxylation of phosphine in alcohol solutions of copper halides

    NASA Astrophysics Data System (ADS)

    Polimbetova, G. S.; Borangazieva, A. K.; Ibraimova, Zh. U.; Bugubaeva, G. O.; Keynbay, S.

    2016-08-01

    The phosphine oxidation reaction with oxygen in alcohol solutions of copper (I, II) halides is studied. Kinetic parameters, intermediates, and by-products are studied by means of NMR 31Р-, IR-, UV-, and ESR- spectroscopy; and by magnetic susceptibility, redox potentiometry, gas chromatography, and elemental analysis. A reaction mechanism is proposed, and the optimum conditions are found for the reaction of oxidative alkoxylation phosphine.

  7. Copper-catalyzed arylation of alkyl halides with arylaluminum reagents

    PubMed Central

    Shrestha, Bijay

    2015-01-01

    Summary We report a Cu-catalyzed coupling between triarylaluminum reagents and alkyl halides to form arylalkanes. The reaction proceeds in the presence of N,N,N’,N’-tetramethyl-o-phenylenediamine (NN-1) as a ligand in combination with CuI as a catalyst. This catalyst system enables the coupling of primary alkyl iodides and bromides with electron-neutral and electron-rich triarylaluminum reagents and affords the cross-coupled products in good to excellent yields. PMID:26734088

  8. Copper-catalyzed arylation of alkyl halides with arylaluminum reagents.

    PubMed

    Shrestha, Bijay; Giri, Ramesh

    2015-01-01

    We report a Cu-catalyzed coupling between triarylaluminum reagents and alkyl halides to form arylalkanes. The reaction proceeds in the presence of N,N,N',N'-tetramethyl-o-phenylenediamine (NN-1) as a ligand in combination with CuI as a catalyst. This catalyst system enables the coupling of primary alkyl iodides and bromides with electron-neutral and electron-rich triarylaluminum reagents and affords the cross-coupled products in good to excellent yields. PMID:26734088

  9. Organolead Halide Perovskites for Low Operating Voltage Multilevel Resistive Switching.

    PubMed

    Choi, Jaeho; Park, Sunghak; Lee, Joohee; Hong, Kootak; Kim, Do-Hong; Moon, Cheon Woo; Park, Gyeong Do; Suh, Junmin; Hwang, Jinyeon; Kim, Soo Young; Jung, Hyun Suk; Park, Nam-Gyu; Han, Seungwu; Nam, Ki Tae; Jang, Ho Won

    2016-08-01

    Organolead halide perovskites are used for low-operating-voltage multilevel resistive switching. Ag/CH3 NH3 PbI3 /Pt cells exhibit electroforming-free resistive switching at an electric field of 3.25 × 10(3) V cm(-1) for four distinguishable ON-state resistance levels. The migration of iodine interstitials and vacancies with low activation energies is responsible for the low-electric-field resistive switching via filament formation and annihilation. PMID:27192161

  10. Lasing in robust cesium lead halide perovskite nanowires

    PubMed Central

    Eaton, Samuel W.; Lai, Minliang; Gibson, Natalie A.; Wong, Andrew B.; Dou, Letian; Ma, Jie; Wang, Lin-Wang; Leone, Stephen R.; Yang, Peidong

    2016-01-01

    The rapidly growing field of nanoscale lasers can be advanced through the discovery of new, tunable light sources. The emission wavelength tunability demonstrated in perovskite materials is an attractive property for nanoscale lasers. Whereas organic–inorganic lead halide perovskite materials are known for their instability, cesium lead halides offer a robust alternative without sacrificing emission tunability or ease of synthesis. Here, we report the low-temperature, solution-phase growth of cesium lead halide nanowires exhibiting low-threshold lasing and high stability. The as-grown nanowires are single crystalline with well-formed facets, and act as high-quality laser cavities. The nanowires display excellent stability while stored and handled under ambient conditions over the course of weeks. Upon optical excitation, Fabry–Pérot lasing occurs in CsPbBr3 nanowires with an onset of 5 μJ cm−2 with the nanowire cavity displaying a maximum quality factor of 1,009 ± 5. Lasing under constant, pulsed excitation can be maintained for over 1 h, the equivalent of 109 excitation cycles, and lasing persists upon exposure to ambient atmosphere. Wavelength tunability in the green and blue regions of the spectrum in conjunction with excellent stability makes these nanowire lasers attractive for device fabrication. PMID:26862172

  11. Quantum Size Effect in Organometal Halide Perovskite Nanoplatelets.

    PubMed

    Sichert, Jasmina A; Tong, Yu; Mutz, Niklas; Vollmer, Mathias; Fischer, Stefan; Milowska, Karolina Z; García Cortadella, Ramon; Nickel, Bert; Cardenas-Daw, Carlos; Stolarczyk, Jacek K; Urban, Alexander S; Feldmann, Jochen

    2015-10-14

    Organometal halide perovskites have recently emerged displaying a huge potential for not only photovoltaic, but also light emitting applications. Exploiting the optical properties of specifically tailored perovskite nanocrystals could greatly enhance the efficiency and functionality of applications based on this material. In this study, we investigate the quantum size effect in colloidal organometal halide perovskite nanoplatelets. By tuning the ratio of the organic cations used, we can control the thickness and consequently the photoluminescence emission of the platelets. Quantum mechanical calculations match well with the experimental values. We find that not only do the properties of the perovskite, but also those of the organic ligands play an important role. Stacking of nanoplatelets leads to the formation of minibands, further shifting the bandgap energies. In addition, we find a large exciton binding energy of up to several hundreds of meV for nanoplatelets thinner than three unit cells, partially counteracting the blueshift induced by quantum confinement. Understanding of the quantum size effects in perovskite nanoplatelets and the ability to tune them provide an additional method with which to manipulate the optical properties of organometal halide perovskites. PMID:26327242

  12. Lasing in robust cesium lead halide perovskite nanowires.

    PubMed

    Eaton, Samuel W; Lai, Minliang; Gibson, Natalie A; Wong, Andrew B; Dou, Letian; Ma, Jie; Wang, Lin-Wang; Leone, Stephen R; Yang, Peidong

    2016-02-23

    The rapidly growing field of nanoscale lasers can be advanced through the discovery of new, tunable light sources. The emission wavelength tunability demonstrated in perovskite materials is an attractive property for nanoscale lasers. Whereas organic-inorganic lead halide perovskite materials are known for their instability, cesium lead halides offer a robust alternative without sacrificing emission tunability or ease of synthesis. Here, we report the low-temperature, solution-phase growth of cesium lead halide nanowires exhibiting low-threshold lasing and high stability. The as-grown nanowires are single crystalline with well-formed facets, and act as high-quality laser cavities. The nanowires display excellent stability while stored and handled under ambient conditions over the course of weeks. Upon optical excitation, Fabry-Pérot lasing occurs in CsPbBr3 nanowires with an onset of 5 μJ cm(-2) with the nanowire cavity displaying a maximum quality factor of 1,009 ± 5. Lasing under constant, pulsed excitation can be maintained for over 1 h, the equivalent of 10(9) excitation cycles, and lasing persists upon exposure to ambient atmosphere. Wavelength tunability in the green and blue regions of the spectrum in conjunction with excellent stability makes these nanowire lasers attractive for device fabrication. PMID:26862172

  13. Deciphering Halogen Competition in Organometallic Halide Perovskite Growth

    DOE PAGESBeta

    Keum, Jong Kahk; Ovchinnikova, Olga S.; Chen, Shiyou; Du, Mao-Hua; Ivanov, Ilia N; Rouleau, Christopher; Geohegan, David B.; Xiao, Kai

    2016-03-01

    Organometallic halide perovskites (OHPs) hold great promise for next-generation, low-cost optoelectronic devices. During the chemical synthesis and crystallization of OHP thin films a major unresolved question is the competition between multiple halide species (e.g. I-, Cl-, Br-) in the formation of the mixed halide perovskite crystals. Whether Cl- ions are successfully incorporated into the perovskite crystal structure or alternatively, where they are located, is not yet fully understood. Here, in situ X-ray diffraction measurements of crystallization dynamics are combined with ex situ TOF-SIMS chemical analysis to reveal that Br- or Cl- ions can promote crystal growth, yet reactive I- ionsmore » prevent them from incorporating into the lattice of the final perovskite crystal structure. The Cl- ions are located in the grain boundaries of the perovskite films. These findings significantly advance our understanding of the role of halogens during synthesis of hybrid perovskites, and provide an insightful guidance to the engineering of high-quality perovskite films, essential for exploring superior-performance and cost-effective optoelectronic devices.« less

  14. Environmental controls over methyl halide emissions from rice paddies

    NASA Astrophysics Data System (ADS)

    Redeker, K. R.; Cicerone, R. J.

    2004-03-01

    This paper examines primary controlling factors that affect methyl halide emissions from rice paddy ecosystems. Observations of four cultivars under multiple growth conditions during studies in commercial fields and the University of California, Irvine, greenhouse lead to the conclusion that daily emissions of methyl halides are primarily determined by the growth stage of the rice plant, with the exception that methyl chloride emissions show no clear seasonal pattern. Methyl chloride emissions appear to be more from the paddy water and/or soil as opposed to the plants; however, in soils with high chloride content, these emissions appear to peak during the reproductive phase. Strong secondary influences include air temperature, soil halide concentration, and soil pore water saturation. The cultivars studied had statistically separate seasonally integrated emissions. Irradiant light and aboveground biomass appear to have little effect on emissions. Emissions of methyl chloride, methyl bromide, and methyl iodide are estimated to be 3.5, 2.3, and 48 mg/m2/yr, or 5.3, 3.5, and 72 Gg/yr, from rice paddies globally.

  15. Deciphering Halogen Competition in Organometallic Halide Perovskite Growth.

    PubMed

    Yang, Bin; Keum, Jong; Ovchinnikova, Olga S; Belianinov, Alex; Chen, Shiyou; Du, Mao-Hua; Ivanov, Ilia N; Rouleau, Christopher M; Geohegan, David B; Xiao, Kai

    2016-04-20

    Organometallic halide perovskites (OHPs) hold great promise for next-generation, low-cost optoelectronic devices. During the chemical synthesis and crystallization of OHP thin films, a major unresolved question is the competition between multiple halide species (e.g., I(-), Cl(-), Br(-)) in the formation of the mixed-halide perovskite crystals. Whether Cl(-) ions are successfully incorporated into the perovskite crystal structure or, alternatively, where they are located is not yet fully understood. Here, in situ X-ray diffraction measurements of crystallization dynamics are combined with ex situ TOF-SIMS chemical analysis to reveal that Br(-) or Cl(-) ions can promote crystal growth, yet reactive I(-) ions prevent them from incorporating into the lattice of the final perovskite crystal structure. The Cl(-) ions are located in the grain boundaries of the perovskite films. These findings significantly advance our understanding of the role of halogens during synthesis of hybrid perovskites and provide an insightful guidance to the engineering of high-quality perovskite films, essential for exploring superior-performing and cost-effective optoelectronic devices. PMID:26931634

  16. Insights from the Adsorption of Halide Ions on Graphene Materials.

    PubMed

    Zhu, Chang; Yang, Gang

    2016-08-18

    Graphene has recently found applications in a wide range of fields. Density functional calculations show that halide ions can be adsorbed on pristine graphene, but only F(-) has an appreciable binding energy (-97.0 kJ mol(-1) ). Graphene materials, which are mainly electron donors, can be made strong electron acceptors by edge functionalization with F atoms. The binding strengths of halide ions are greatly enhanced by edge functionalization and show direct proportionality with the degree of functionalization Θ and increased charge transfer. In contrast, the adsorption strengths of metal ions on pristine graphene are clearly superior to those of halide ions but decline substantially with increasing degree of edge functionalization, and for Θ=100 %, the binding energies of -95.7, -44.8, and -25.9 kJ mol(-1) that are calculated for Li(+) , Na(+) , and K(+) , respectively, are obviously inferior to that of F(-) (-186.3 kJ mol(-1) ). Thus, the electronic properties of graphene are fundamentally regulated by edge functionalization, and the preferential adsorption of certain metal ions or anions can be facilely realized by choice of an appropriate degree of functionalization. Adsorbed metal ions and anions behave differently on gradual addition of water molecules, and their binding strengths remain substantial when graphene materials are in the pristine and highly edge functionalized states, respectively. PMID:27127939

  17. Depth profile of halide anions under highly charged biological membrane

    NASA Astrophysics Data System (ADS)

    Sung, Woongmo; Wang, Wenjie; Lee, Jonggwan; Vaknin, David; Kim, Doseok

    2015-03-01

    Halide ion (Cl- and I-) distribution under a cationic Langmuir monolayer consisting of 1,2-dipalmitoyl-3 trimethylammonium-propane (DPTAP) molecules was investigated by vibrational sum-frequency generation (VSFG) and X-ray spectroscopy. From VSFG spectra, it was observed that large halide anions (I-) screen surface charge more efficiently so that interfacial water alignment becomes more randomized. On the other hand, number density of ions directly measured by X-ray fluorescence spectroscopy at grazing incidence angle reveals that the ion densities within 6 ~ 8 nm are the same for both I- and Cl-. Since the observed ion densities in both cases are almost equal to the charge density of the DPTAP monolayer, we propose that larger halide anions are attracted closer to the surface making direct binding with the charged headgroups of the molecules in the monolayer, accomplishing charge neutrality in short distance. This direct adsorption of anions also disturbs the monolayer structure both in terms of the conformation of alkyl chains and the vertical configuration of the monolayer, with iodine having the stronger effect. Our study shows that the length scale that ions neutralize a charged interface varies significantly and specifically even between monovalent ions.

  18. Iodomethane-Mediated Organometal Halide Perovskite with Record Photoluminescence Lifetime.

    PubMed

    Xu, Weidong; McLeod, John A; Yang, Yingguo; Wang, Yimeng; Wu, Zhongwei; Bai, Sai; Yuan, Zhongcheng; Song, Tao; Wang, Yusheng; Si, Junjie; Wang, Rongbin; Gao, Xingyu; Zhang, Xinping; Liu, Lijia; Sun, Baoquan

    2016-09-01

    Organometallic lead halide perovskites are excellent light harvesters for high-efficiency photovoltaic devices. However, as the key component in these devices, a perovskite thin film with good morphology and minimal trap states is still difficult to obtain. Herein we show that by incorporating a low boiling point alkyl halide such as iodomethane (CH3I) into the precursor solution, a perovskite (CH3NH3PbI3-xClx) film with improved grain size and orientation can be easily achieved. More importantly, these films exhibit a significantly reduced amount of trap states. Record photoluminescence lifetimes of more than 4 μs are achieved; these lifetimes are significantly longer than that of pristine CH3NH3PbI3-xClx films. Planar heterojunction solar cells incorporating these CH3I-mediated perovskites have demonstrated a dramatically increased power conversion efficiency compared to the ones using pristine CH3NH3PbI3-xClx. Photoluminescence, transient absorption, and microwave detected photoconductivity measurements all provide consistent evidence that CH3I addition increases the number of excitons generated and their diffusion length, both of which assist efficient carrier transport in the photovoltaic device. The simple incorporation of alkyl halide to enhance perovskite surface passivation introduces an important direction for future progress on high efficiency perovskite optoelectronic devices. PMID:27529636

  19. Extensive and Highly Accurate Line Lists for Hydrogen Halides

    NASA Astrophysics Data System (ADS)

    Li, G.; Bernath, P. F.; Gordon, I. E.; Rothman, L. S.; Richard, C.; Le Roy, R. J.; Coxon, J. A.; Hajigeorgiou, P.

    2011-06-01

    New dipole moment functions (DMF) for the ground X 1Σ+ electronic states of the hydrogen halides (HF, HCl, HBr, HI) have been obtained using a direct fit approach that fits the best available and appropriately weighted experimental line intensity data for individual ro-vibrational transitions. Combining the newly developed (taking into account the most recent experiments) empirical potential energy functions and the DMFs, line positions and line intensities of the hydrogen halides and their isotopologues have been calculated numerically using program LEVEL. In addition, new semi-empirical algorithms for assigning line-shape parameters for these species have been developed. Using these improvements, new line lists for hydrogen halides were created to update the HITRAN spectroscopic database. These new lists are more accurate and significantly more extensive than those included in the current version of the database (HITRAN2008). R.J. Le Roy, ``LEVEL 8.0, 2007'', University of Waterloo Chemical Physics Research Report CP-663 (2007); see http://leroy.uwaterloo.ca/programs/. L.S. Rothman, I.E. Gordon, A. Barbe, D.C. Benner, P.F. Bernath, et al., ``The HITRAN 2008 Molecular Spectroscopic Database,'' JQSRT 110, 532-572 (2009).

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

    NASA Astrophysics Data System (ADS)

    Lammert, Heiko; Heuer, Andreas

    2005-12-01

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

  1. Method for the safe disposal of alkali metal

    DOEpatents

    Johnson, Terry R.

    1977-01-01

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

  2. Indirect detection of halide ions via fluorescence quenching of quinine sulfate in microcolumn ion chromatography.

    PubMed

    Takeuchi, Toyohide; Sumida, Junichi

    2004-06-01

    Halide ions could be visualized via fluorescence quenching in microcolumn ion chromatography. The fluorescence of quinine sulfate, which was contained in an acidic eluent, was quenched by halide ions. The observed fluorescence quenching values increased in this order: iodide, bromide, and chloride. The present detection system was relatively sensitive to halide ions except for fluoride: other anions gave smaller signals than halide ions. The present detection system provided quantitative information, so it could be applied to the determination of chloride in water samples. PMID:15228124

  3. Method for producing hydrocarbon fuels from heavy polynuclear hydrocarbons by use of molten metal halide catalyst

    DOEpatents

    Gorin, Everett

    1979-01-01

    In a process for hydrocracking heavy polynuclear carbonaceous feedstocks to produce lighter hydrocarbon fuels by contacting the heavy feedstocks with hydrogen in the presence of a molten metal halide catalyst, thereafter separating at least a substantial portion of the carbonaceous material associated with the reaction mixture from the spent molten metal halide and thereafter regenerating the metal halide catalyst, an improvement comprising contacting the spent molten metal halide catalyst after removal of a major portion of the carbonaceous material therefrom with an additional quantity of hydrogen is disclosed.

  4. Systematic analysis of the unique band gap modulation of mixed halide perovskites.

    PubMed

    Kim, Jongseob; Lee, Sung-Hoon; Chung, Choong-Heui; Hong, Ki-Ha

    2016-02-14

    Solar cells based on organic-inorganic hybrid metal halide perovskites have been proven to be one of the most promising candidates for the next generation thin film photovoltaic cells. Mixing Br or Cl into I-based perovskites has been frequently tried to enhance the cell efficiency and stability. One of the advantages of mixed halides is the modulation of band gap by controlling the composition of the incorporated halides. However, the reported band gap transition behavior has not been resolved yet. Here a theoretical model is presented to understand the electronic structure variation of metal mixed-halide perovskites through hybrid density functional theory. Comparative calculations in this work suggest that the band gap correction including spin-orbit interaction is essential to describe the band gap changes of mixed halides. In our model, both the lattice variation and the orbital interactions between metal and halides play key roles to determine band gap changes and band alignments of mixed halides. It is also presented that the band gap of mixed halide thin films can be significantly affected by the distribution of halide composition. PMID:26791587

  5. Determination of the common and rare alkalies in mineral analysis

    USGS Publications Warehouse

    Wells, R.C.; Stevens, R.E.

    1934-01-01

    Methods are described which afford a determination of each member of the alkali group and are successful in dealing with the quantities of the rare alkalies found in rocks and minerals. The procedures are relatively rapid and based chiefly on the use of chloroplatinic acid, absolute alcohol and ether, and ammonium sulfate. The percentages of all the alkalies found in a number of minerals are given.

  6. Environmental mercury contamination around a chlor-alkali plant

    SciTech Connect

    Lodenius, M.; Tulisalo, E.

    1984-04-01

    The chlor-alkali industry is one of the most important emitters of mercury. This metal is effectively spread from chlor-alkali plants into the atmosphere and it has been reported that only a few percent of the mercury emissions are deposited locally the major part spreading over very large areas. The purpose of this investigation was to study the spreading of mercury up to 100 km from a chlor-alkali plant using three different biological indicators.

  7. Superconductivity in doped fullerenes

    SciTech Connect

    Hebard, A.F. )

    1992-11-01

    While there is not complete agreement on the microscopic mechanism of superconductivity in alkali-metal-doped C[sub 60], further research may well lead to the production of analogous materials that lose resistance at even higher temperatures. Carbon 60 is a fascinating and arrestingly beautiful molecule. With 12 pentagonal and 20 hexagonal faces symmetrically arrayed in a soccer-ball-like structure that belongs to the icosahedral point group, I[sub h], its high symmetry alone invites special attention. The publication in September 1990 of a simple technique for manufacturing and concentrating macroscopic amounts of this new form of carbon announced to the scientific community that enabling technology had arrived. Macroscopic amounts of C[sub 60] (and the higher fullerenes, such as C[sub 70] and C[sub 84]) can now be made with an apparatus as simple as an arc furnace powered with an arc welding supply. Accordingly, chemists, physicists and materials scientists have joined forces in an explosion of effort to explore the properties of this unusual molecular building block. 23 refs., 6 figs.

  8. Electrochemical devices utilizing molten alkali metal electrode-reactant

    DOEpatents

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

    1985-07-10

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

  9. Electrochemical devices utilizing molten alkali metal electrode-reactant

    DOEpatents

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

    1986-01-01

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

  10. Abiotic Formation of Methyl Halides in the Terrestrial Environment

    NASA Astrophysics Data System (ADS)

    Keppler, F.

    2011-12-01

    Methyl chloride and methyl bromide are the most abundant chlorine and bromine containing organic compounds in the atmosphere. Since both compounds have relatively long tropospheric lifetimes they can effectively transport halogen atoms from the Earth's surface, where they are released, to the stratosphere and following photolytic oxidation form reactive halogen gases that lead to the chemical destruction of ozone. Methyl chloride and methyl bromide account for more than 20% of the ozone-depleting halogens delivered to the stratosphere and are predicted to grow in importance as the chlorine contribution to the stratosphere from anthropogenic CFCs decline. Today methyl chloride and methyl bromide originate mainly from natural sources with only a minor fraction considered to be of anthropogenic origin. However, until as recently as 2000 most of the methyl chloride and methyl bromide input to the atmosphere was considered to originate from the oceans, but investigations in recent years have clearly demonstrated that terrestrial sources such as biomass burning, wood-rotting fungi, coastal salt marshes, tropical vegetation and organic matter degradation must dominate the atmospheric budgets of these trace gases. However, many uncertainties still exist regarding strengths of both sources and sinks, as well as the mechanisms of formation of these naturally occurring halogenated gases. A better understanding of the atmospheric budget of both methyl chloride and methyl bromide is therefore required for reliable prediction of future ozone depletion. Biotic and abiotic methylation processes of chloride and bromide ion are considered to be the dominant pathways of formation of these methyl halides in nature. In this presentation I will focus on abiotic formation processes in the terrestrial environment and the potential parameters that control their emissions. Recent advances in our understanding of the abiotic formation pathway of methyl halides will be discussed. This will

  11. Long-lived charge carrier dynamics in polymer/quantum dot blends and organometal halide perovskites

    NASA Astrophysics Data System (ADS)

    Nagaoka, Hirokazu

    Solution-processable semiconductors offer a potential route to deploy solar panels on a wide scale, based on the possibility of reduced manufacturing costs by using earth-abundant materials and inexpensive production technologies, such as inkjet or roll-to-roll printing. Understanding the fundamental physics underlying device operation is important to realize this goal. This dissertation describes studies of two kinds of solar cells: hybrid polymer/PbS quantum dot solar cells and organometal halide perovskite solar cells. Chapter two discusses details of the experimental techniques. Chapter three and four explore the mechanisms of charge transfer and energy transfer spectroscopically, and find that both processes contribute to the device photocurrent. Chapter four investigates the important question of how the energy level alignment of quantum dot acceptors affects the operation of hybrid polymer/quantum dot solar cells, by making use of the size-tunable energy levels of PbS quantum dots. We observe that long-lived charge transfer yield is diminished at larger dot sizes as the energy level offset at the polymer/quantum dot interface is changed through decreasing quantum confinement using a combination of spectroscopy and device studies. Chapter five discusses the effects of TiO2 surface chemistry on the performance of organometal halide perovskite solar cells. Specifically, chapter five studies the effect of replacing the conventional TiO2 electrode with Zr-doped TiO2 (Zr-TiO2). We aim to explore the correlation between charge carrier dynamics and device studies by incorporating zirconium into TiO2. We find that, compared to Zr-free controls, solar cells employing Zr-TiO2 give rise to an increase in overall power conversion efficiency, and a decrease in hysteresis. We also observe longer carrier lifetimes and higher charge carrier densities in devices on Zr-TiO2 electrodes at microsecond times in transient photovoltage experiments, as well as at longer persistent

  12. Electrodes For Alkali-Metal Thermoelectric Converters

    NASA Technical Reports Server (NTRS)

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

    1989-01-01

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

  13. High power diode pumped alkali vapor lasers

    NASA Astrophysics Data System (ADS)

    Zweiback, J.; Krupke, B.

    2008-05-01

    Diode pumped alkali lasers have developed rapidly since their first demonstration. These lasers offer a path to convert highly efficient, but relatively low brightness, laser diodes into a single high power, high brightness beam. General Atomics has been engaged in the development of DPALs with scalable architectures. We have examined different species and pump characteristics. We show that high absorption can be achieved even when the pump source bandwidth is several times the absorption bandwidth. In addition, we present experimental results for both potassium and rubidium systems pumped with a 0.2 nm bandwidth alexandrite laser. These data show slope efficiencies of 67% and 72% respectively.

  14. Cathode architectures for alkali metal / oxygen batteries

    SciTech Connect

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

    2015-01-13

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

  15. Water in the hydration shell of halide ions has significantly reduced Fermi resonance and moderately enhanced Raman cross section in the OH stretch regions.

    PubMed

    Ahmed, Mohammed; Singh, Ajay K; Mondal, Jahur A; Sarkar, Sisir K

    2013-08-22

    Water in the presence of electrolytes plays an important role in biological and industrial processes. The properties of water, such as the intermolecular coupling, Fermi resonance (FR), hydrogen-bonding, and Raman cross section were investigated by measuring the Raman spectra in the OD and OH stretch regions in presence of alkali halides (NaX; X = F, Cl, Br, I). It is observed that the changes in spectral characteristics by the addition of NaX in D2O are similar to those obtained by the addition of H2O in D2O. The spectral width decreases significantly by the addition of NaX in D2O (H2O) than that in the isotopically diluted water. Quantitative estimation, on the basis of integrated Raman intensity, revealed that the relative Raman cross section, σ(H)/σ(b) (σ(H) and σ(b) are the average Raman cross section of water in the first hydration shell of X(-) and in bulk, respectively), in D2O and H2O is higher than those in the respective isotopically diluted water. These results suggest that water in the hydration shell has reduced FR and intermolecular coupling compared to those in bulk. In the isotopically diluted water, the relative Raman cross section increases with increase in size of the halide ions (σ(H)/σ(b) = 0.6, 1.1, 1.5, and 1.9 for F(-), Cl(-), Br(-), and I(-), respectively), which is assignable to the enhancement of Raman cross section by charge transfer from halide ions to the hydrating water. Nevertheless, the experimentally determined σ(H)/σ(b) is lower than the calculated values obtained on the basis of the energy of the charge transfer state of water. The weak enhancement of σ(H)/σ(b) signifies that the charge transfer transition in the hydration shell of halide ions causes little change in the OD (OH) bond lengths of hydrating water. PMID:23895453

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

    PubMed

    Chen, Fangfang; Forsyth, Maria

    2016-07-28

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

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

    NASA Technical Reports Server (NTRS)

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

    1993-01-01

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

  18. Multiband effects on the superconductivity in doped C[sub 60

    SciTech Connect

    Choi, H. ); Rice, M.J. )

    1994-03-01

    We consider multiband effects on the superconductivity in the alkali-doped fullerenes. It is shown that the multiband superconducting gap is reduced to the well-known Bardeen-Cooper-Schrieffer expression due to a cyclic symmetry in the orientationally ordered phases, thereby justifying many previous works assuming single-band [ital s]-wave pairing without considering several conduction bands explicitly.

  19. An assessment of Mercury immobilisation in alkali activated fly ash (AAFA) cements.

    PubMed

    Donatello, Shane; Fernández-Jiménez, Ana; Palomo, Angel

    2012-04-30

    This paper presents total and soluble Mercury contents for three coal fly ashes and alkali-activated fly ash (AAFA) cements consisting of 100% fly ash as starting material. To evaluate the potential of the AAFA cement matrix to immobilise Hg from an external source, another batch of cements, doped with 5000 mg/kg Hg as highly soluble HgCl(2), was prepared. The ashes and control AAFA cements complied with Mercury leaching criteria for non-hazardous wastes according to both TCLP and EN 12457 tests. Fly ash activated cements doped with 5000 mg/kg Hg and aged for 2 days immobilised 98.8-99.6% and 97.3-98.8% of Hg according to TCLP and EN 12457 tests respectively. Evidence from SEM-EDX suggests that Hg was immobilised by precipitation as highly insoluble HgS or Hg(2)S, although partial precipitation as less insoluble HgO or Hg silicates could not be entirely ruled out based on data presented. The results for Hg-doped cements contribute to the growing body of evidence that shows AAFA cement as a useful material for immobilizing elevated concentrations of toxic and hazardous elements. PMID:22341491

  20. Interaction of alkali metals with perylene-3,4,9,10- tetracarboxylic-dianhydride thin films

    SciTech Connect

    Wuesten, J.; Berger, S.; Heimer, K.; Lach, S.; Ziegler, Ch.

    2005-07-01

    n doping of the molecular organic semiconductor perylene-3,4,9,10-tetracarboxylic-dianhydride (PTCDA) is often achieved by use of alkali metals as dopants. This doping process is commonly performed in two steps. In the first the dopant is evaporated onto the surface of the PTCDA film. As it has been believed that the dopant shows an inhomogeneous diffusion profile through the layer with most of the dopant accumulated in the first few layers, a subsequent annealing step has been performed in order to reach a homogeneous distribution of the dopant in the whole layer. In this paper experimental results concerning chemical composition ((angle resolved) X-ray photoemission spectroscopy, secondary-ion-mass spectrometry, Fourier transform infrared spectroscopy), electronic structure (ultraviolet photoemission spectroscopy, inverse photoemission spectroscopy), as well as electrical properties (conductivity, Seebeck coefficient) are shown before and after doping and before and after annealing. These results suggest that the deposited dopant is redistributed and partially removed during the annealing step. A model for the dopant distribution is suggested.

  1. Superconductivity in alkali metal intercalated iron selenides.

    PubMed

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

    2016-07-27

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

  2. Durability of Alkali Activated Blast Furnace Slag

    NASA Astrophysics Data System (ADS)

    Ellis, K.; Alharbi, N.; Matheu, P. S.; Varela, B.; Hailstone, R.

    2015-11-01

    The alkali activation of blast furnace slag has the potential to reduce the environmental impact of cementitious materials and to be applied in geographic zones where weather is a factor that negatively affects performance of materials based on Ordinary Portland Cement. The scientific literature provides many examples of alkali activated slag with high compressive strengths; however research into the durability and resistance to aggressive environments is still necessary for applications in harsh weather conditions. In this study two design mixes of blast furnace slag with mine tailings were activated with a potassium based solution. The design mixes were characterized by scanning electron microscopy, BET analysis and compressive strength testing. Freeze-thaw testing up to 100 freeze-thaw cycles was performed in 10% road salt solution. Our findings included compressive strength of up to 100 MPa after 28 days of curing and 120 MPa after freeze-thaw testing. The relationship between pore size, compressive strength, and compressive strength after freeze-thaw was explored.

  3. Superconductivity in alkali metal intercalated iron selenides

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

  4. Decalcification resistance of alkali-activated slag.

    PubMed

    Komljenović, Miroslav M; Baščarević, Zvezdana; Marjanović, Nataša; Nikolić, Violeta

    2012-09-30

    This paper analyses the effects of decalcification in concentrated 6M NH(4)NO(3) solution on mechanical and microstructural properties of alkali-activated slag (AAS). Portland-slag cement (CEM II/A-S 42.5 N) was used as a benchmark material. Decalcification process led to a decrease in strength, both in AAS and in CEM II, and this effect was more pronounced in CEM II. The decrease in strength was explicitly related to the decrease in Ca/Si atomic ratio of C-S-H gel. A very low ratio of Ca/Si ~0.3 in AAS was the consequence of coexistence of C-S-H(I) gel and silica gel. During decalcification of AAS almost complete leaching of sodium and tetrahedral aluminum from C-S-H(I) gel also took place. AAS showed significantly higher resistance to decalcification in relation to the benchmark CEM II due to the absence of portlandite, high level of polymerization of silicate chains, low level of aluminum for silicon substitution in the structure of C-S-H(I), and the formation of protective layer of polymerized silica gel during decalcification process. In stabilization/solidification processes alkali-activated slag represents a more promising solution than Portland-slag cement due to significantly higher resistance to decalcification. PMID:22818592

  5. Dynamics of reactive ultracold alkali polar molecules

    NASA Astrophysics Data System (ADS)

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

    2011-05-01

    Recently, ultracold polar molecules of KRb have been created. These molecules are chemically reactive and their lifetime in a trap is limited. However, their lifetime increases when they are loaded into a 1D optical lattice in the presence of an electric field. These results naturally raise the question of manipulating ultracold collisions of other species of alkali dimer molecules, with an eye toward both novel stereochemistry, as well as suppressing unwanted reactions, to enable condensed matter applications. In this talk, we report on a comparative study between the bi-alkali polar molecules of LiNa, LiK, LiRb, LiCs which have been predicted to be reactive. We compute the isotropic C6 coefficients of these systems and we predict the elastic and reactive rate coefficients when an electric field is applied in a 1D optical lattice. We will discuss the efficacy of evaporative cooling for each species. This work was supported by a MURI-AFOSR grant.

  6. Artificial Synapses: Organometal Halide Perovskite Artificial Synapses (Adv. Mater. 28/2016).

    PubMed

    Xu, Wentao; Cho, Himchan; Kim, Young-Hoon; Kim, Young-Tae; Wolf, Christoph; Park, Chan-Gyung; Lee, Tae-Woo

    2016-07-01

    A synapse-emulating electronic device based on organometal halide perovskite thin films is described by T.-W. Lee and co-workers on page 5916. The device successfully emulates important characteristics of a biological synapse. This work extends the application of organometal halide perovskites to bioinspired electronic devices, and contributes to the development of neuromorphic electronics. PMID:27442971

  7. EPA (ENVIRONMENTAL PROTECTION AGENCY) METHOD STUDY 32: METHOD 450.1 - TOTAL ORGANIC HALIDES (TOX)

    EPA Science Inventory

    The report describes the interlaboratory method study that was performed to evaluate interim Method 450.1 for total organic halides (TOX). In the method, a measured volume of water is passed through two columns in series each containing 40 mg of activated charcoal. Organic halide...

  8. Aryl-triazole foldamers incorporating a pyridinium motif for halide anion binding in aqueous media.

    PubMed

    Shang, Jie; Zhao, Wei; Li, Xichen; Wang, Ying; Jiang, Hua

    2016-03-15

    Aryl-triazole oligomers incorporating a pyridinium motif have been synthesized from their pyridine precursors. Anion binding studies show that methylation of the pyridine units can significantly enhance the halide anion affinities of the folded oligomers so that the foldamers are capable of binding halide anions in aqueous solutions. PMID:26933696

  9. 75 FR 5544 - Energy Conservation Program: Energy Conservation Standards for Metal Halide Lamp Fixtures: Public...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-02-03

    ... public meeting and availability of the Framework Document in the Federal Register (74 FR 69036) for... for Metal Halide Lamp Fixtures: Public Meeting and Availability of the Framework Document AGENCY... conservation standards for certain metal halide lamp fixtures. This document announces that the period...

  10. Thermal battery. [solid metal halide electrolytes with enhanced electrical conductance after a phase transition

    DOEpatents

    Carlsten, R.W.; Nissen, D.A.

    1973-03-06

    The patent describes an improved thermal battery whose novel design eliminates various disadvantages of previous such devices. Its major features include a halide cathode, a solid metal halide electrolyte which has a substantially greater electrical conductance after a phase transition at some temperature, and a means for heating its electrochemical cells to activation temperature.

  11. THE DETERMINATION OF TOTAL ORGANIC HALIDE IN WATER: AN INTERLABORATORY COMPARATIVE STUDY OF TWO METHODS

    EPA Science Inventory

    Total organic halide (TOX) analyzers are commonly used to measure the amount of dissolved halogenated organic byproducts in disinfected waters. Because of the lack of information on the identity of disinfection byproducts, rigorous testing of the dissolved organic halide (DOX) pr...

  12. THE DETERMINATION OF TOTAL ORGANIC HALIDE IN WATER: A COMPARATIVE STUDY OF TWO INSTRUMENTS

    EPA Science Inventory

    Total organic halide (TOX) analyzers are commonly used to measure the amount of dissolved halogenated organic byproducts in disinfected waters. ecause of the lack of information on the identity of disinfection byproducts, rigorous testing of the dissolved organic halide (DOX) pro...

  13. Nanostructured Lanthanum Halides and CeBr3 for Nuclear Radiation and Detection

    SciTech Connect

    Paul Guss, Sanjoy Mukhopadhyay, Ron Guise, Ding Yuan

    2010-06-09

    Scintillator materials are used to detect, and in some cases identify, gamma rays. Higher performance scintillators are expensive, hard to manufacture, fragile, and sometimes require liquid nitrogen or cooling engines. But whereas lower-quality scintillators are cheap, easy to manufacture, and more rugged, their performance is lower. At issue: can the desirable qualities of high-and low-performance scintillators be combined to achieve better performance at lower cost? Preliminary experiments show that a LaF{sub 3}:Ce oleic acid-based nanocomposite exhibits a photopeak when exposed to {sup 137}Cs source gamma-radiation. The chemical synthesis of the cerium-doped lanthanum halide nanoparticles are scalable and large quantities of material can be produced at a time, unlike typical crystal growth processes such as the Bridgeman process. Using a polymer composite (Figure 1), produced by LANL, initial measurements of the unloaded and 8% LaF{sub 3}:Ce-loaded sample have been made using {sup 137}Cs sources. Figure 2 shows an energy spectrum acquired for CeF{sub 3}. The lighter plot is the measured polymer-only spectrum and the black plot is the spectrum from the nanocomposite scintillator. As the development of this material continues, the energy resolution is expected to improve and the photopeak-to-Compton ratio will become greater at higher loadings. These measurements show the expected Compton edge in the polymer-only sample, and the Compton edge and photo-peak expected in the nanophosphor composites that LANL has produced. Using a porous VYCORR with CdSe/ZnS core shell quantum dots, Letant has demonstrated that he has obtained signatures of the 241Am photopeak with energy resolution as good at NaI (Figure 3). We begin with the fact that CeBr{sub 3} crystals do not have a self-activity component as strong as the lanthanum halides. The radioactive 0.090% {sup 138}La component of lanthanum leads to significant self-activity, which will be a problem for very large

  14. 40 CFR 721.8900 - Substituted halogenated pyridinol, alkali salt.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ..., alkali salt. 721.8900 Section 721.8900 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.8900 Substituted halogenated pyridinol, alkali salt. (a) Chemical..., chemical destruction and carbon adsorption. (iv) Release to water. Requirements as specified in § 721.90...

  15. Formation of lysinoalanine in egg white under alkali treatment.

    PubMed

    Zhao, Yan; Luo, Xuying; Li, Jianke; Xu, Mingsheng; Tu, Yonggang

    2016-03-01

    To investigate the formation mechanism of lysinoalanine (LAL) in eggs during the alkali treatment process, NaOH was used for the direct alkali treatment of egg white, ovalbumin, and amino acids; in addition, the amount of LAL formed during the alkali treatment process was measured. The results showed that the alkali treatment resulted in the formation of LAL in the egg white. The LAL content increased with increasing pH and temperature, with the LAL content first increasing and then leveling off with increasing time. The amount of LAL formed in the ovalbumin under the alkali treatment condition accounted for approximately 50.51% to 58.68% of the amount of LAL formed in the egg white. Thus, the LAL formed in the ovalbumin was the main source for the LAL in the egg white during the alkali treatment process. Under the alkali treatment condition, free L-serine, L-cysteine, and L-cystine reacted with L-lysine to form LAL; therefore, they are the precursor amino acids of LAL formed in eggs during the alkali treatment process. PMID:26772660

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

    DOEpatents

    Soung, Wen Y.

    1984-01-01

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

  17. 40 CFR 721.4740 - Alkali metal nitrites.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

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

  18. 40 CFR 721.4740 - Alkali metal nitrites.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

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

  19. 40 CFR 721.4740 - Alkali metal nitrites.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

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

  20. 40 CFR 721.4740 - Alkali metal nitrites.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

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

  1. Self-discharge in bimetallic cells containing alkali metal

    NASA Technical Reports Server (NTRS)

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

    1969-01-01

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

  2. COMPLEX FLUORIDES OF PLUTONIUM AND AN ALKALI METAL

    DOEpatents

    Seaborg, G.T.

    1960-08-01

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

  3. 40 CFR 721.4740 - Alkali metal nitrites.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

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

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

    Code of Federal Regulations, 2010 CFR

    2010-07-01

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

  5. Method for producing hydrocarbon fuels and fuel gas from heavy polynuclear hydrocarbons by the use of molten metal halide catalysts

    DOEpatents

    Gorin, Everett

    1979-01-01

    In a process for hydrocracking heavy polynuclear carbonaceous feedstocks to produce lighter hydrocarbon fuels by contacting the heavy feedstocks with hydrogen in the presence of a molten metal halide catalyst in a hydrocracking zone, thereafter separating at least a major portion of the lighter hydrocarbon fuels from the spent molten metal halide and thereafter regenerating the spent molten metal halide by incinerating the spent molten metal halide by combustion of carbon and sulfur compounds in the spent molten metal halide in an incineration zone, the improvement comprising: (a) contacting the heavy feedstocks and hydrogen in the presence of the molten metal halide in the hydrocracking zone at reaction conditions effective to convert from about 60 to about 90 weight percent of the feedstock to lighter hydrocarbon fuels; (b) separating at least a major portion of the lighter hydrocarbon fuels from the spent molten metal halide; (c) contacting the spent molten metal halide with oxygen in a liquid phase gasification zone at a temperature and pressure sufficient to vaporize from about 25 to about 75 weight percent of the spent metal halide, the oxygen being introduced in an amount sufficient to remove from about 60 to about 90 weight percent of the carbon contained in the spent molten metal halide to produce a fuel gas and regenerated metal halide; and (d) incinerating the spent molten metal halide by combusting carbon and sulfur compounds contained therein.

  6. Effects of alkali treatments on Ag nanowire transparent conductive films

    NASA Astrophysics Data System (ADS)

    Kim, Sunho; Kang, Jun-gu; Eom, Tae-yil; Moon, Bongjin; Lee, Hoo-Jeong

    2016-06-01

    In this study, we employ various alkali materials (alkali metals with different base strengths, and ammonia gas and solution) to improve the conductivity of silver nanowire (Ag NW)-networked films. The alkali treatment appears to remove the surface oxide and improve the conductivity. When applied with TiO2 nanoparticles, the treatment appears more effective as the alkalis gather around wire junctions and help them weld to each other via heat emitted from the reduction reaction. The ammonia solution treatment is found to be quick and aggressive, damaging the wires severely in the case of excessive treatment. On the other hand, the ammonia gas treatment seems much less aggressive and does not damage the wires even after a long exposure. The results of this study highlight the effectiveness of the alkali treatment in improving of the conductivity of Ag NW-networked transparent conductive films.

  7. Performance of Straight Steel Fibres Reinforced Alkali Activated Concrete

    NASA Astrophysics Data System (ADS)

    Faris, Meor Ahmad; Bakri Abdullah, Mohd Mustafa Al; Nizar Ismail, Khairul; Muniandy, Ratnasamy; Putra Jaya, Ramadhansyah

    2016-06-01

    This paper focus on the performance of alkali activated concrete produced by using fly ash activated by sodium silicate and sodium hydroxide solutions. These alkali activated concrete were reinforced with straight steel fibres with different weight percentage starting from 0 % up to 5 %. Chemical composition of raw material in the production alkali activated concrete which is fly ash was first identified by using X-ray fluorescence. Results reveal there have an effect of straight steel fibres inclusion to the alkali activated concrete. Highest compressive strength of alkali activated concrete which is 67.72 MPa was obtained when 3 % of straight fibres were added. As well as flexural strength, highest flexural strength which is 6.78 MPa was obtained at 3 % of straight steel fibres inclusions.

  8. Methyl Halide Production by Periphyton Mats from the Florida Everglades

    NASA Astrophysics Data System (ADS)

    Raffel, A.; Jones, R. D.; Rice, A. L.; Scully, N. M.

    2012-12-01

    Methyl chloride and methyl bromide are trace gases with both natural and anthropogenic origins. Once generated these gases transport chlorine and bromine into the stratosphere, where they play an important role in atmospheric chemistry by participating in ozone depleting catalytic cycles. Coastal wetlands are one location where methyl halide emissions have been proposed to be elevated due to high primary production and ionic halogens. This region also provides a unique study environment due to salt water intrusions which occur during storm or low marsh water level-high tide events. The purpose of this research was to determine how varying concentrations of salinity affect methyl halide production originating from periphyton mats within the Florida Everglades. Florida Everglades periphyton (25 g/L) were exposed to continuous 12 hour dark/light cycles in varying concentrations of salt water (0, 0.1, 1.0, and 10‰). All water samples were analyzed to determine the concentration and production rate of methyl chloride and methyl bromide in periphyton samples using a gas chromatograph coupled with an electron capture detector. The concentration of methyl chloride increased by approximately 3.4 and 60 pM over a 0 to 72 hour range for 1‰ and 10 ‰ treatments respectively, and reached a steady state concentration after 24 hours. There was no significant production of methyl bromide for all treatments. These studies will be used to gain a better understanding of methyl halide production from periphyton mats in simulated natural conditions. This research was supported by the National Science Foundation Chemical Oceanography Program Award No. 1029710.

  9. New generation of medium wattage metal halide lamps and spectroscopic tools for their diagnostics

    NASA Astrophysics Data System (ADS)

    Dunaevsky, A.; Tu, J.; Gibson, R.; Steere, T.; Graham, K.; van der Eyden, J.

    2010-11-01

    A new generation of ceramic metal halide high intensity discharge (HID) lamps has achieved high efficiencies by implementing new design concepts. The shape of the ceramic burner is optimized to withstand high temperatures with minimal thermal stress. Corrosion processes with the ceramic walls are slowed down via adoption of non-aggressive metal halide chemistry. Light losses over life due to tungsten deposition on the walls are minimized by maintaining a self-cleaning chemical process, known as tungsten cycle. All these advancements have made the new ceramic metal halide lamps comparable to high pressure sodium lamps for luminous efficacy, life, and maintenance while providing white light with high color rendering. Direct replacement of quartz metal halide lamps and systems results in the energy saving from 18 up to 50%. High resolution spectroscopy remains the major non-destructive tool for the ceramic metal halide lamps. Approaches to reliable measurements of relative partial pressures of the arc species are discussed.

  10. Impact of the organic halide salt on final perovskite composition for photovoltaic applications

    SciTech Connect

    Moore, David T.; Sai, Hiroaki; Wee Tan, Kwan; Estroff, Lara A.; Wiesner, Ulrich

    2014-08-01

    The methylammonium lead halide perovskites have shown significant promise as a low-cost, second generation, photovoltaic material. Despite recent advances, however, there are still a number of fundamental aspects of their formation as well as their physical and electronic behavior that are not well understood. In this letter we explore the mechanism by which these materials crystallize by testing the outcome of each of the reagent halide salts. We find that components of both salts, lead halide and methylammonium halide, are relatively mobile and can be readily exchanged during the crystallization process when the reaction is carried out in solution or in the solid state. We exploit this fact by showing that the perovskite structure is formed even when the lead salt's anion is a non-halide, leading to lower annealing temperature and time requirements for film formation. Studies into these behaviors may ultimately lead to improved processing conditions for photovoltaic films.

  11. Volatile species in halide-activated-diffusion coating packs

    NASA Technical Reports Server (NTRS)

    Bianco, Robert; Rapp, Robert A.; Jacobson, Nathan S.

    1992-01-01

    An atmospheric pressure sampling mass spectrometer was used to identify the vapor species generated in a halide-activated cementation pack. Pack powder mixtures containing a Cr-Al binary masteralloy powder, an NH4Cl activator salt, and either ZrO2 or Y2O3 (or neither) were analyzed at 1000 C. Both the equilibrium calculations for the pack and mass spectrometer results indicated that volatile AlCl(x) and CrCl(y) species were generated by the pack powder mixture; in packs containing the reactive element oxide, volatile ZrCl(z) and YCl(w) species were formed by the conversion of their oxide sources.

  12. Silylaryl Halides Can Replace Triflates as Aryne Precursors.

    PubMed

    Mesgar, Milad; Daugulis, Olafs

    2016-08-01

    Silylaryl bromides and iodides can be prepared in one step from commercially available starting materials. Arynes can be generated from these compounds under conditions nearly identical to those employed for silylaryl triflates. Three distinct transformations, ortho-arylation of N-tritylanilines, intermolecular addition of arynes to amides, and reaction of ureas with arynes, were shown to be successful for the new aryne precursors. The main advantage of silylaryl halides relative to silyl aryl triflates is their one-step preparation from commercially available starting materials. PMID:27415183

  13. Heavy ion passive dosimetry with silver halide single crystals

    NASA Technical Reports Server (NTRS)

    Childs, C. B.; Parnell, T. A.

    1972-01-01

    A method of detecting radiation damage tracks due to heavy particles in large single crystals of the silver halides is described. The tracks, when made visible with a simple electrical apparatus, appear similar to tracks in emulsions. The properties of the crystals, the technique of printing out the tracks, and evidence concerning the threshold energy for registering particles indicates that this method may find application in heavy ion dosimetry. The method has been found to be sensitive to stopping He nuclei and relativistic M group cosmic rays. Some impurities strongly influence the printout of the tracks, and the effects of these impurities are discussed.

  14. Optical Properties of Photovoltaic Organic-Inorganic Lead Halide Perovskites.

    PubMed

    Green, Martin A; Jiang, Yajie; Soufiani, Arman Mahboubi; Ho-Baillie, Anita

    2015-12-01

    Over the last several years, organic-inorganic lead halide perovskites have rapidly emerged as a new photovoltaic contender. Although energy conversion efficiency above 20% has now been certified, improved understanding of the material properties contributing to these high performance levels may allow the progression to even higher efficiency, stable cells. The optical properties of these new materials are important not only to device design but also because of the insight they provide into less directly accessible properties, including energy-band structures, binding energies, and likely impact of excitons, as well as into absorption and inverse radiative recombination processes. PMID:26560862

  15. Thermal conductivity of halide solid solutions: measurement and prediction.

    PubMed

    Gheribi, Aïmen E; Poncsák, Sándor; St-Pierre, Rémi; Kiss, László I; Chartrand, Patrice

    2014-09-14

    The composition dependence of the lattice thermal conductivity in NaCl-KCl solid solutions has been measured as a function of composition and temperature. Samples with systematically varied compositions were prepared and the laser flash technique was used to determine the thermal diffusivity from 373 K to 823 K. A theoretical model, based on the Debye approximation of phonon density of state (which contains no adjustable parameters) was used to predict the thermal conductivity of both stoichiometric compounds and fully disordered solid solutions. The predictions obtained with the model agree very well with our measurement. A general method for predicting the thermal conductivity of different halide systems is discussed. PMID:25217938

  16. Ferroelectricity and Rashba-type band splittings in metal halides

    NASA Astrophysics Data System (ADS)

    Kim, Minsung; Im, Jino; Freeman, Arthur; Ihm, Jisoon; Jin, Hosub

    2014-03-01

    In this study, we investigate Rashba-type band splittings in metal halides. We use a minimal tight-binding model and first principles calculations based on density functional theory to understand the electronic structures of the materials. We find that different types of Rashba bands occur in the conduction and valence band edges in terms of the angular momentum textures. Also, the characteristics of the band splittings will be discussed in connection with the ferroelectric property. Department of Physics and Astronomy, Seoul National University, Seoul 151-747, Korea.

  17. "XA6" octahedra influencing the arrangement of anionic groups and optical properties in inverse-perovskite [B6O10]XA3 (X = Cl, Br; A = alkali metal).

    PubMed

    Yang, Zhihua; Lei, Bing-Hua; Yang, Bin; Pan, Shilie

    2016-06-01

    Exploring the effect of microscopic units, which set up the perovsikte framework, is of importance for material design. In this study, a series of borate halides with inverse-perovskite structures [B6O10]XA3 (X = Cl, Br; A = alkali metal) have been studied. It was revealed that the distortion and volume of XA6 octahedra influence the arrangement of anionic groups, which leads to the flexibility of the perovskite-related framework and differences in optical properties. Under the structural control scheme, the structure of Rb3B6O10Cl was predicted. The stability of the predicted structure was confirmed by an ab initio density functional theory-based method. The calculation shows Rb3B6O10Cl has a short UV cutoff edge of less than 200 nm, a moderate birefringence and a large second harmonic generation response. PMID:27211304

  18. Diversity and Mechanisms of Alkali Tolerance in Lactobacilli▿

    PubMed Central

    Sawatari, Yuki; Yokota, Atsushi

    2007-01-01

    We determined the maximum pH that allows growth (pHmax) for 34 strains of lactobacilli. High alkali tolerance was exhibited by strains of Lactobacillus casei, L. paracasei subsp. tolerans, L. paracasei subsp. paracasei, L. curvatus, L. pentosus, and L. plantarum that originated from plant material, with pHmax values between 8.5 and 8.9. Among these, L. casei NRIC 1917 and L. paracasei subsp. tolerans NRIC 1940 showed the highest pHmax, at 8.9. Digestive tract isolates of L. gasseri, L. johnsonii, L. reuteri, L. salivarius subsp. salicinius, and L. salivarius subsp. salivarius exhibited moderate alkali tolerance, with pHmax values between 8.1 and 8.5. Dairy isolates of L. delbrueckii subsp. bulgaricus, L. delbrueckii subsp. lactis, and L. helveticus exhibited no alkali tolerance, with pHmax values between 6.7 and 7.1. Measurement of the internal pH of representative strains revealed the formation of transmembrane proton gradients (ΔpH) in a reversed direction (i.e., acidic interior) at alkaline external-pH ranges, regardless of their degrees of alkali tolerance. Thus, the reversed ΔpH did not determine alkali tolerance diversity. However, the ΔpH contributed to alkali tolerance, as the pHmax values of several strains decreased with the addition of nigericin, which dissipates ΔpH. Although neutral external-pH values resulted in the highest glycolysis activity in the presence of nigericin regardless of alkali tolerance, substantial glucose utilization was still detected in the alkali-tolerant strains, even in a pH range of between 8.0 and 8.5, at which the remaining strains lost most activity. Therefore, the alkali tolerance of glycolysis reactions contributes greatly to the determination of alkali tolerance diversity. PMID:17449704

  19. EPR study of polarons in a conducting polymer with nondegenerate ground states: Alkali metal complexes of poly (p-phenylene) and phenylene oligomers

    SciTech Connect

    Kispert, L.D.; Joseph, J.; Miller, G.G.; Baughman, R.H.

    1984-08-15

    EPR measurements are used to characterize electronic states relevant for carrier transport in alkali metal doped poly(p-phenylene), PPP, fully deuterated poly(p-phenylene), DPPP, and phenylene oligomers. Observed spin concentrations per carbon are at least one decade higher than the Curie spin concentration for Na-doped polyacetylene. The number of these spins, which likely corresponds to polarons (mobile radical anions), is much less than the amount of alkali metal dopant, suggesting that much of the charge on the polymer chains is in bipolarons (spinless dianions). Relevant to the interaction between spins on the polymer chain and the metal cations, the observed g values are close to the free electron value and do not substantially vary with the donor dopant, temperature, or the molecular weight of the phenylene chain. Although the spin-orbit effect on g values is small, room temperature linewidth tends to increase with increasing atomic number of dopant: suggesting some interaction, albeit a smaller magnitude effect than for alkali-metal graphite complexes. The EPR linewidths are exchange narrowed and proton hyperfine broadening is significant. The latter explains the generally broader linewidths for doped PPP than for doped DPPP. The measured susceptibilities have a temperature dependence which suggests equilibrium between separated polaron defects and singlet and triplet spin states formed intermolecularly via polaron pairing. The interaction is antiferromagnetic and the binding energy between polarons is about 2.2 to 3.3 meV. An upper limit estimate of the Fermi-surface density of states for K-doped PPP (0.7 states/eV phenyl) is derived from an upper limit estimate of Pauli susceptibility.

  20. Adsorption of hydrated halide ions on charged electrodes. Molecular dynamics simulation

    NASA Astrophysics Data System (ADS)

    Glosli, James N.; Philpott, Michael R.

    1993-06-01

    Constant temperature molecular dynamics has been used to simulate the adsorption of hydrated halide ions X-=F-, Cl-, Br- and I-, and lithium ion Li+ on flat uniformly charged surfaces. The simulations were done with either 214 water molecules and two ions (Li+ and X-) in a box 2.362 nm deep or with 430 water molecules and the two ions in a box 4.320 nm deep. The boxes were periodically replicated in the xy directions. The magnitude of the surface charge on the box ends was ±0.11 e/(nm)2, corresponding to an electric field of 2×107 V/cm. The lateral dimensions of the simulation cell were 1.862 nm×1.862 nm (x×y) in each case. All of the water molecules and ions interacted with the end walls via a weak 9-3 potential. The Stillinger ST2 water model and parameters optimized for alkali halides interacting with the model ST2 water molecule were used in the calculations. Common particles of truncating the interactions at a finite distance (0.82 nm) and switching off Coulomb interactions at small distances were followed. The temperature was set at T=2.411 kJ/mol (290 K). Some of the properties calculated were distribution density profiles for ions and water across the gap important for comparisons with Gouy-Chapman theory, adsorbed ion-water pair correlation functions, and the number of water molecules in the first and second hydration shells of the ions as a function of time. The time spent by a water molecule in the hydration shell was calculated to be approximately ten times longer for lithium than any other ion. The correlation between distance from the electrode and hydration number was studied and generally found to be pronounced for the larger anions. Comparison of the dynamics of the common ion Li+ for different anions revealed the subtle influence of a transcell interaction in the 2.362 nm thick film. In the given field, the smallest ions Li+ and F- remained fully solvated at all times. Chloride behaved quite differently. Part of the time this ion was far