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Sample records for alkali halide solutions

  1. 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.

  2. 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

  3. 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.

  4. 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.

  5. 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

  6. 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

  7. 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.

  8. 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.

  9. 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…

  10. 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.

  11. 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.

  12. 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

  13. 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.

  14. 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.

  15. 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.

  16. 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%.

  17. 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

  18. 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.

  19. 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.

  20. 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.

  1. 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

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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)

  7. 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.

  8. 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

  9. 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

  10. 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.

  11. 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).

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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

  12. 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.

  13. 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

  14. 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.

  15. 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

  16. 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 .

  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. 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.

  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. 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.

  2. 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

  3. 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.

  4. 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.

  5. 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)

  6. 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

  7. 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.

  8. 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

  9. 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

  10. 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.

  11. 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.

  12. 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.

  13. 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

  14. Oxide Film Aging on Alloy 22 in Halide Containing Solutions

    SciTech Connect

    Rodriguez, Martin A.; Carranza, Ricardo M.; Rebak, Raul B.

    2007-07-01

    Passive and corrosion behaviors of Alloy 22 in chloride and fluoride containing solutions, changing the heat treatment of the alloy, the halide concentration and the pH of the solutions at 90 deg. C, was investigated. The study was implemented using electrochemical techniques, which included open circuit potential monitoring over time, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) measurements carried out at open circuit and at passivity potentials. Corrosion rates obtained by EIS measurements after 24 h immersion in naturally aerated solutions were below 0.5 {mu}m/year. The corrosion rates were practically independent of solution pH, alloy heat treatment and halide ion nature and concentration. EIS low frequency resistance values increased with applied potential in the passive domain and with polarization time in pH 6 - 1 M NaCl at 90 deg. C. This effect was attributed to an increase in the oxide film thickness and oxide film aging. High frequency capacitance measurements indicated that passive oxide on Alloy 22 presented a double n-type/p-type semiconductor behavior in the passive potential range. (authors)

  15. 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

  16. 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

  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. 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

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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 +}.

  7. 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

  8. 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.

  9. 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.

  10. Hydrogen bonded structure of water and aqueous solutions of sodium halides: a Raman spectroscopic study

    NASA Astrophysics Data System (ADS)

    Li, Ruihua; Jiang, Zhanpeng; Chen, Fengen; Yang, Hongwei; Guan, Yuntao

    2004-11-01

    The OH stretching (2500-4000 cm -1) Raman spectra from pure water and sodium halides solutions are obtained. The Raman contours are deconvoluted with five Gaussian components that their center frequencies are 3051, 3233, 3393, 3511 and 3628 cm -1, respectively. From the Raman spectra and their deconvolutions similarities and differences of the effects of temperature and sodium halides on hydrogen bond structure of water are shown clearly. Like temperature, all of sodium halides break tetrahedral structure of water, and the Gaussian component of 3233 cm -1 decreases and the components of 3393 and 3511 cm -1 increase basically. The differences lie in their effects on the component 3051 and 3628 cm -1. All of halogenic ions break tetrahedral structure of water and their breaking actions are in the order of F -1

  11. Cellulose aerogels from aqueous alkali hydroxide-urea solution.

    PubMed

    Cai, Jie; Kimura, Satoshi; Wada, Masahisa; Kuga, Shigenori; Zhang, Lina

    2008-01-01

    Highly porous and strong cellulose aerogels were prepared by gelation of cellulose from aqueous alkali hydroxide/urea solution, followed by drying with supercritical CO2. Their morphology, pore structure, and physical properties were characterized by scanning and transmission electron microscopy, X-ray diffraction, nitrogen adsorption measurements, UV/Vis spectrometry, and tensile tests. The cellulose hydrogel was composed of interconnected about 20 nm wide. By using supercritical CO2 drying, the network structure in the hydrogel was well preserved in the aerogel. The results are preliminary but demonstrate the ability of this method to give cellulose aerogels of large surface areas (400-500 m2 g(-1)) which may be useful as adsorbents, heat/sound insulators, filters, catalyst supports, or carbon aerogel precursors. PMID:18605678

  12. 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.

  13. 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

  14. 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.

  15. 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.

  16. Solvation structure around ruthenium(II) tris(bipyridine) in lithium halide solutions

    PubMed Central

    Josefsson, Ida; Eriksson, Susanna K.; Rensmo, Håkan; Odelius, Michael

    2016-01-01

    The solvation of the ruthenium(II) tris(bipyridine) ion ([Ru(bpy)3]2+) is investigated with molecular dynamics simulations of lithium halide solutions in polar solvents. The anion distribution around the [Ru(bpy)3]2+ complex exhibits a strong solvent dependence. In aqueous solution, the iodide ion forms a solvent shared complex with [Ru(bpy)3]2+, but not in the other solvents. Between Cl– and [Ru(bpy)3]2+, the strong hydration of the chloride ion results in a solvent separated complex where more than one solvent molecule separates the anion from the metal center. Hence, tailored solvation properties in electrolytes is a route to influence ion-ion interactions and related electron transfer processes. PMID:26798838

  17. Theoretical estimation of solvation parameters and interfacial tension of clusters of potassium halides in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Polak, W.; Sangwal, K.

    1996-03-01

    Using the model of the formation of ionic clusters, an analytical equation valid for the equilibrium concentration of solute in the solution is derived. Employing Boltzmann statistics in conjunction with the experimental values of the equilibrium concentration of KF, KCl, KBr and KI electrolytes in aqueous solution at 25°C, the above analytical equation is used to compute the best values of the dielectric permittivity of the solvation shell for the K + ion and four anions separately. These values of the dielectric permittivity of the solvation shells are then used to compute adsorption energy of water molecules on the {100} surface of regular clusters and their surface tension in the solution as functions of type of the salt, its concentration and cluster size. It is found that both the average adsorption energy and the interfacial tension of regular clusters composed of i ions can be approximated by a linear function of i - {1}/{2} for different concentrations of all the investigated potassium halides, and that, depending on the concentration of the solutions, the surface tension of regular clusters in solutions can increase or decrease with their size.

  18. Textures on the surface of BSA films with different concentrations of sodium halides and water state in solution

    NASA Astrophysics Data System (ADS)

    Glibitskiy, Gennadiy; Glibitskiy, Dmitriy; Gorobchenko, Olga; Nikolov, Oleg; Roshal, Alexander; Semenov, Mikhail; Gasan, Anatoliy

    2015-03-01

    The formation of the textures on the surface of the films from the solutions of bovine serum albumin (BSA) with sodium halides (NaF, NaCl, and NaBr) of various concentrations was studied. The formation of symmetric zigzag textures on the surface of BSA films (Cryst Eng 3:173-194, 2000) in the presence of sodium halides depends on the conformational state of the protein globule. Thermal denaturation of BSA also did not allow to form zigzag textures on the surface of the films.

  19. 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

  20. 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

  1. Laboratory determination of the carbon kinetic isotope effects (KIEs) for reactions of methyl halides with various nucleophiles in solution

    USGS Publications Warehouse

    Baesman, S.M.; Miller, L.G.

    2005-01-01

    Large carbon kinetic isotope effects (KIEs) were measured for reactions of methyl bromide (MeBr), methyl chloride (MeCl), and methyl iodide (MeI) with various nucleophiles at 287 and 306 K in aqueous solutions. Rates of reaction of MeBr and MeI with H2O (neutral hydrolysis) or Cl- (halide substitution) were consistent with previous measurements. Hydrolysis rates increased with increasing temperature or pH (base hydrolysis). KIEs for hydrolysis were 51 ?? 6??? for MeBr and 38 ?? 8??? for MeI. Rates of halide substitution increased with increasing temperature and greater reactivity of the attacking nucleophile, with the fastest reaction being that of MeI with Br-. KIEs for halide substitution were independent of temperature but varied with the reactant methyl halide and the attacking nucleophile. KIEs were similar for MeBr substitution with Cl- and MeCl substitution with Br- (57 ?? 5 and 60 ?? 9??? respectively). The KIE for halide exchange of MeI was lower overall (33 ?? 8??? and was greater for substitution with Br- (46 ?? 6???) than with Cl- (29 ?? 6???). ?? Springer Science + Business Media, Inc. 2005.

  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. Thermal transport properties of halide solid solutions: Experiments vs equilibrium molecular dynamics.

    PubMed

    Gheribi, Aïmen E; Salanne, Mathieu; Chartrand, Patrice

    2015-03-28

    The composition dependence of thermal transport properties of the (Na,K)Cl rocksalt solid solution is investigated through equilibrium molecular dynamics (EMD) simulations in the entire range of composition and the results are compared with experiments published in recent work [Gheribi et al., J. Chem. phys. 141, 104508 (2014)]. The thermal diffusivity of the (Na,K)Cl solid solution has been measured from 473 K to 823 K using the laser flash technique, and the thermal conductivity was deduced from critically assessed data of heat capacity and density. The thermal conductivity was also predicted at 900 K in the entire range of composition by a series of EMD simulations in both NPT and NVT statistical ensembles using the Green-Kubo theory. The aim of the present paper is to provide an objective analysis of the capability of EMD simulations in predicting the composition dependence of the thermal transport properties of halide solid solutions. According to the Klemens-Callaway [P. G. Klemens, Phys. Rev. 119, 507 (1960) and J. Callaway and H. C. von Bayer, Phys. Rev. 120, 1149 (1960)] theory, the thermal conductivity degradation of the solid solution is explained by mass and strain field fluctuations upon the phonon scattering cross section. A rigorous analysis of the consistency between the theoretical approach and the EMD simulations is discussed in detail. PMID:25833567

  4. Thermal transport properties of halide solid solutions: Experiments vs equilibrium molecular dynamics

    SciTech Connect

    Gheribi, Aïmen E. Chartrand, Patrice; Salanne, Mathieu

    2015-03-28

    The composition dependence of thermal transport properties of the (Na,K)Cl rocksalt solid solution is investigated through equilibrium molecular dynamics (EMD) simulations in the entire range of composition and the results are compared with experiments published in recent work [Gheribi et al., J. Chem. phys. 141, 104508 (2014)]. The thermal diffusivity of the (Na,K)Cl solid solution has been measured from 473 K to 823 K using the laser flash technique, and the thermal conductivity was deduced from critically assessed data of heat capacity and density. The thermal conductivity was also predicted at 900 K in the entire range of composition by a series of EMD simulations in both NPT and NVT statistical ensembles using the Green-Kubo theory. The aim of the present paper is to provide an objective analysis of the capability of EMD simulations in predicting the composition dependence of the thermal transport properties of halide solid solutions. According to the Klemens-Callaway [P. G. Klemens, Phys. Rev. 119, 507 (1960) and J. Callaway and H. C. von Bayer, Phys. Rev. 120, 1149 (1960)] theory, the thermal conductivity degradation of the solid solution is explained by mass and strain field fluctuations upon the phonon scattering cross section. A rigorous analysis of the consistency between the theoretical approach and the EMD simulations is discussed in detail.

  5. 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)

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

    PubMed

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

    2015-04-01

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

  7. Role of hydrogen bonding in solubility of poly(N-isopropylacrylamide) brushes in sodium halide solutions

    NASA Astrophysics Data System (ADS)

    Xin-Jun, Zhao; Zhi-Fu, Gao

    2016-07-01

    By employing molecular theory, we systematically investigate the shift of solubility of poly(N-isopropylacrylamide) (PNIPAM) brushes in sodium halide solutions. After considering PNIPAM–water hydrogen bonds, water–anion hydrogen bonds, and PNIPAM–anion bonds and their explicit coupling to the PNIPAM conformations, we find that increasing temperature lowers the solubility of PNIPAM, and results in a collapse of the layer at high enough temperatures. The combination of the three types of bonds would yield a decrease in the solubility of PNIPAM following the Hofmeister series: NaCl>NaBr>NaI. PNIPAM–water hydrogen bonds are affected by water–anion hydrogen bonds and PNIPAM–anion bonds. The coupling of polymer conformations and the competition among the three types of bonds are essential for describing correctly a decrease in the solubility of PNIPAM brushes, which is determined by the free energy associated with the formation of the three types of bonds. Our results agree well with the experimental observations, and would be very important for understanding the shift of the lower critical solution temperature of PNIPAM brushes following the Hofmeister series. Project supported by the National Natural Science Foundation of China (Grant Nos. 21264016, 11464047, and 21364016) and the Joint Funds of Xinjiang Natural Science Foundation, China (Grant No. 2015211C298).

  8. Relativistic and Solvation Effects on the Stability of Gold(III) Halides in Aqueous Solution.

    PubMed

    Theilacker, Kolja; Schlegel, H Bernhard; Kaupp, Martin; Schwerdtfeger, Peter

    2015-10-19

    The redox stability of gold halide complexes in aqueous solution has been examined quantum-chemically by a systematic comparison of scalar- and nonrelativistic pseudopotential calculations, using both COSMO and D-COSMO-RS solvent models for water. After a computational benchmarking of density-functional methods against CCSD(T) results for the gas phase decomposition AuX4(-) → AuX2(-) + X2, B3LYP calculations have been used to establish solvent contributions. While relativity clearly enhances the stability of AuX4(-) (X = F, Cl, Br, I) complexes against X2 elimination, solvation favors the lower oxidation state. Solvation and relativity are nonadditive, due to the relativistic reduction of bond polarity. At scalar relativistic D-COSMO-RS level, the reaction AuX4(-) ⇌ AuX2(-) + X2 is computed to be endergonic, except for X = I, where it is slightly exergonic. Under the chosen conditions, partial hydrolysis of AuCl4(-) to AuCl3OH(-) is exergonic. The latter complex in turn is stable against Cl2 elimination. The disproportionation 3 AuCl2(-) ⇌ AuCl4(-) + 2 Au(s) + 2 Cl(-) is clearly exergonic. All of the computed reaction energies at scalar relativistic D-COSMO-RS level agree well with the observed speciation in dilute pH-neutral solutions at ambient temperatures. PMID:26421633

  9. Using Perovskite Nanoparticles as Halide Reservoirs in Catalysis and as Spectrochemical Probes of Ions in Solution.

    PubMed

    Doane, Tennyson L; Ryan, Kayla L; Pathade, Laxmikant; Cruz, Kevin J; Zang, Huidong; Cotlet, Mircea; Maye, Mathew M

    2016-06-28

    The ability of cesium lead halide (CsPbX3; X = Cl(-), Br(-), I(-)) perovskite nanoparticles (P-NPs) to participate in halide exchange reactions, to catalyze Finkelstein organohalide substitution reactions, and to colorimetrically monitor chemical reactions and detect anions in real time is described. With the use of tetraoctylammonium halide salts as a starting point, halide exchange with the P-NPs was performed to calibrate reactivity, stability, and extent of ion exchange. The exchange of CsPbI3 with Cl(-) or Br(-) causes a significant blue-shift in absorption and photoluminescence, whereas reacting I(-) with CsPbBr3 causes a red-shift of similar magnitudes. With the high local halide concentrations and the facile nature of halide exchange in mind, we then explored the ability of P-NPs to catalyze organohalide exchange in Finkelstein like reactions. Results indicate that the P-NPs serve as excellent halide reservoirs for substitution of organohalides in nonpolar media, leading to not only different organohalide products, but also a complementary color change over the course of the reaction, which can be used to monitor kinetics in a precise manner. The merits of using P-NP as spectrochemical probes for real time assaying is then expanded to other anions which can react with, or result in unique, classes of perovskites. PMID:27149396

  10. 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

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

    NASA Astrophysics Data System (ADS)

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

    2014-06-01

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

  12. High Photoluminescence Efficiency and Optically Pumped Lasing in Solution-Processed Mixed Halide Perovskite Semiconductors.

    PubMed

    Deschler, Felix; Price, Michael; Pathak, Sandeep; Klintberg, Lina E; Jarausch, David-Dominik; Higler, Ruben; Hüttner, Sven; Leijtens, Tomas; Stranks, Samuel D; Snaith, Henry J; Atatüre, Mete; Phillips, Richard T; Friend, Richard H

    2014-04-17

    The study of the photophysical properties of organic-metallic lead halide perovskites, which demonstrate excellent photovoltaic performance in devices with electron- and hole-accepting layers, helps to understand their charge photogeneration and recombination mechanism and unravels their potential for other optoelectronic applications. We report surprisingly high photoluminescence (PL) quantum efficiencies, up to 70%, in these solution-processed crystalline films. We find that photoexcitation in the pristine CH3NH3PbI3-xClx perovskite results in free charge carrier formation within 1 ps and that these free charge carriers undergo bimolecular recombination on time scales of 10s to 100s of ns. To exemplify the high luminescence yield of the CH3NH3PbI3-xClx perovskite, we construct and demonstrate the operation of an optically pumped vertical cavity laser comprising a layer of perovskite between a dielectric mirror and evaporated gold top mirrors. These long carrier lifetimes together with exceptionally high luminescence yield are unprecedented in such simply prepared inorganic semiconductors, and we note that these properties are ideally suited for photovoltaic diode operation. PMID:26269988

  13. Alkali Treatment of Acidic Solution from Hanford K Basin Sludge Dissolution

    SciTech Connect

    AA Bessonov; AB Yusov; AM Fedoseev; AV Gelis; AY Garnov; CH Delegard; GM Plavnik; LN Astafurova; MS Grigoriev; NA Budantseva; NN Krot; SI Nikitenko; TP Puraeva; VP Perminov; VP Shilov

    1998-12-22

    Nitric acid solutions will be created from the dissolution of Hanford K Basin sludge. These acidic dissolver solutions must be made alkaline by treatment with NaOH solution before they are disposed to ~ the Tank Waste Remediation System on the Hanford Site. During the alkali treatments, sodium diuranate, hydroxides of iron and aluminum, and radioelements (uranium, plutonium, and americium) will precipitate from the dissolver solution. Laboratory tests, discussed here, were pefiormed to provide information on these precipitates and their precipitation behavior that is important in designing the engineering flowsheet for the treatment process. Specifically, experiments were conducted to determine the optimum precipitation conditions; the completeness of uranium, plutonium, and americium precipitation; the rate of sedimentation; and the physico-chemical characteristics of the solids formed by alkali treatment of simulated acidic dissolver solutions. These experiments also determined the redistribution of uranium, plutonium, and americium flom the sodium di~ate and iron and al&inurn hydroxide precipitates upon contact with carbonate- and EDTA-bearing simulated waste solutions. Note: EDTA is the tetrasodium salt of ethylenediaminetetraacetate.

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

    PubMed

    Jeliński, Tomasz; Cysewski, Piotr

    2016-06-01

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

  15. Blue-Green Color Tunable Solution Processable Organolead Chloride-Bromide Mixed Halide Perovskites for Optoelectronic Applications.

    PubMed

    Sadhanala, Aditya; Ahmad, Shahab; Zhao, Baodan; Giesbrecht, Nadja; Pearce, Phoebe M; Deschler, Felix; Hoye, Robert L Z; Gödel, Karl C; Bein, Thomas; Docampo, Pablo; Dutton, Siân E; De Volder, Michael F L; Friend, Richard H

    2015-09-01

    Solution-processed organo-lead halide perovskites are produced with sharp, color-pure electroluminescence that can be tuned from blue to green region of visible spectrum (425-570 nm). This was accomplished by controlling the halide composition of CH3NH3Pb(BrxCl1-x)3 [0 ≤ x ≤ 1] perovskites. The bandgap and lattice parameters change monotonically with composition. The films possess remarkably sharp band edges and a clean bandgap, with a single optically active phase. These chloride-bromide perovskites can potentially be used in optoelectronic devices like solar cells and light emitting diodes (LEDs). Here we demonstrate high color-purity, tunable LEDs with narrow emission full width at half maxima (FWHM) and low turn on voltages using thin-films of these perovskite materials, including a blue CH3NH3PbCl3 perovskite LED with a narrow emission FWHM of 5 nm. PMID:26236949

  16. Blue-Green Color Tunable Solution Processable Organolead Chloride–Bromide Mixed Halide Perovskites for Optoelectronic Applications

    PubMed Central

    2015-01-01

    Solution-processed organo-lead halide perovskites are produced with sharp, color-pure electroluminescence that can be tuned from blue to green region of visible spectrum (425–570 nm). This was accomplished by controlling the halide composition of CH3NH3Pb(BrxCl1–x)3 [0 ≤ x ≤ 1] perovskites. The bandgap and lattice parameters change monotonically with composition. The films possess remarkably sharp band edges and a clean bandgap, with a single optically active phase. These chloride–bromide perovskites can potentially be used in optoelectronic devices like solar cells and light emitting diodes (LEDs). Here we demonstrate high color-purity, tunable LEDs with narrow emission full width at half maxima (FWHM) and low turn on voltages using thin-films of these perovskite materials, including a blue CH3NH3PbCl3 perovskite LED with a narrow emission FWHM of 5 nm. PMID:26236949

  17. 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.

  18. Low-frequency dynamics of aqueous alkali chloride solutions as probed by terahertz spectroscopy

    NASA Astrophysics Data System (ADS)

    Kann, Z. R.; Skinner, J. L.

    2016-06-01

    Terahertz (far infrared) spectroscopy provides a useful tool for probing both ionic motions in solution and the effect of ionic solutes on the dynamics of the solvent. In this study, we calculate terahertz spectra of aqueous alkali chloride solutions using classical but novel (the water model includes three-body interactions, the ion parameterization is non-standard, and the dipole surface is polarizable) molecular dynamics simulations. The calculated spectra compare reasonably well to experimental spectra. Decomposition of the calculated spectra is used to gain a deeper understanding of the physical phenomena underlying the spectra and the connection to, for instance, the vibrational density of states for the ions. The decomposed results are also used to explain many of the cation-dependent trends observed in the experimental spectra.

  19. The effects of lithium hydroxide solution on alkali silica reaction gels created with opal

    SciTech Connect

    Mitchell, Lyndon D.; Beaudoin, James J.; Grattan-Bellew, Patrick

    2004-04-01

    The reaction of Nevada opal with calcium hydroxide, potassium hydroxide and lithium hydroxide solutions was investigated. In addition, opal was exposed to a combined solution of these three hydroxides. The progress of the three reactions was followed using X-ray diffraction (XRD), {sup 29}Si nuclear magnetic resonance (NMR) and scanning electron microscopy (SEM). The XRD results indicated the presence of a low-angle peak exclusive to the lithium-based reactions. The NMR results suggested a change in the silicate structure in the presence of lithium. These techniques indicated that the reaction of the alkali with the opal starting material is inhibited and perhaps stopped in the presence of lithium hydroxide. SEM revealed that the morphology of the reaction products on the surface of the reacted opal grains is markedly different invariably. It was concluded that evidence to support the theory of a protective layer exists and that the nature of the layer varies with ion type.

  20. Surface charge density on silica in alkali and alkaline earth chloride electrolyte solutions

    NASA Astrophysics Data System (ADS)

    Dove, Patricia M.; Craven, Colin M.

    2005-11-01

    The surface charge density of colloidal SiO 2 (Aerosil 380) was measured in alkali chloride (0.067 and 0.20 M LiCl, NaCl, and KCl) and alkaline earth chloride (0.067 M MgCl 2, CaCl 2, SrCl 2, BaCl 2) solutions. Measurements were conducted at 25°C by potentiometric titrations using the constant ionic medium method in a CO 2-free system. The experimental design measured surface charge for solutions with constant ionic strength as well as constant cation concentration. Alkali chloride solutions promote negative surface charge density in the order LiCl < NaCl < KCl to give the "regular" lyotropic behavior previously reported. In contrast, the alkaline earth chloride solutions exhibit a reversed lyotropic trend with increasing crystallographic radius where increasing negative charge is promoted in the order BaCl 2 < SrCl 2 < CaCl 2 < MgCl 2. The origin of the opposing affinity trends is probed by testing the hypothesis that this reversal is rooted in the differing solvent structuring characteristics of the IA and IIA cations at the silica-water interface. This idea arises from earlier postulations that solvent structuring effects increase entropy through solvent disordering and these gains must be much greater than the small, positive enthalpy associated with electrostatic interactions. By correlating measured charge density with a proxy for the solvent-structuring ability of cations, this study shows that silica surface charge density is maximized by those electrolytes that have the strongest effects on solvent structuring. We suggest that for a given solid material, solvation entropy has a role in determining the ionic specificity of electrostatic interactions and reiterate the idea that the concept of lyotropy is rooted in the solvent-structuring ability of cations at the interface.

  1. Tunable room-temperature spin-selective optical Stark effect in solution-processed layered halide perovskites

    PubMed Central

    Giovanni, David; Chong, Wee Kiang; Dewi, Herlina Arianita; Thirumal, Krishnamoorthy; Neogi, Ishita; Ramesh, Ramamoorthy; Mhaisalkar, Subodh; Mathews, Nripan; Sum, Tze Chien

    2016-01-01

    Ultrafast spin manipulation for opto–spin logic applications requires material systems that have strong spin-selective light-matter interaction. Conventional inorganic semiconductor nanostructures [for example, epitaxial II to VI quantum dots and III to V multiple quantum wells (MQWs)] are considered forerunners but encounter challenges such as lattice matching and cryogenic cooling requirements. Two-dimensional halide perovskite semiconductors, combining intrinsic tunable MQW structures and large oscillator strengths with facile solution processability, can offer breakthroughs in this area. We demonstrate novel room-temperature, strong ultrafast spin-selective optical Stark effect in solution-processed (C6H4FC2H4NH3)2PbI4 perovskite thin films. Exciton spin states are selectively tuned by ~6.3 meV using circularly polarized optical pulses without any external photonic cavity (that is, corresponding to a Rabi energy of ~55 meV and equivalent to applying a 70 T magnetic field), which is much larger than any conventional system. The facile halide and organic replacement in these perovskites affords control of the dielectric confinement and thus presents a straightforward strategy for tuning light-matter coupling strength. PMID:27386583

  2. Tunable room-temperature spin-selective optical Stark effect in solution-processed layered halide perovskites.

    PubMed

    Giovanni, David; Chong, Wee Kiang; Dewi, Herlina Arianita; Thirumal, Krishnamoorthy; Neogi, Ishita; Ramesh, Ramamoorthy; Mhaisalkar, Subodh; Mathews, Nripan; Sum, Tze Chien

    2016-06-01

    Ultrafast spin manipulation for opto-spin logic applications requires material systems that have strong spin-selective light-matter interaction. Conventional inorganic semiconductor nanostructures [for example, epitaxial II to VI quantum dots and III to V multiple quantum wells (MQWs)] are considered forerunners but encounter challenges such as lattice matching and cryogenic cooling requirements. Two-dimensional halide perovskite semiconductors, combining intrinsic tunable MQW structures and large oscillator strengths with facile solution processability, can offer breakthroughs in this area. We demonstrate novel room-temperature, strong ultrafast spin-selective optical Stark effect in solution-processed (C6H4FC2H4NH3)2PbI4 perovskite thin films. Exciton spin states are selectively tuned by ~6.3 meV using circularly polarized optical pulses without any external photonic cavity (that is, corresponding to a Rabi energy of ~55 meV and equivalent to applying a 70 T magnetic field), which is much larger than any conventional system. The facile halide and organic replacement in these perovskites affords control of the dielectric confinement and thus presents a straightforward strategy for tuning light-matter coupling strength. PMID:27386583

  3. Structure of Solvated Mercury(II) Halides in Liquid Ammonia, Triethyl Phosphite And Tri-N-Butylphosphine Solution

    SciTech Connect

    Nilsson, Kersti B.; Maliarik, Mikhail; Persson, Ingmar; Sandstrom, Magnus

    2009-05-22

    Liquid ammonia, trialkyl phosphites, and especially trialkylphosphines, are very powerful electron-pair donor solvents with soft bonding character. The solvent molecules act as strongly coordinating ligands towards mercury(ii), interacting strongly enough to displace halide ligands. In liquid ammonia mercury(ii) chloride solutions separate into two liquid phases; the upper contains tetraamminemercury(ii) complexes, [Hg(NH(3))(4)](2+), and chloride ions in low concentration, while the lower is a dense highly concentrated solution of [Hg(NH(3))(4)](2+) entities, ca. 1.4 mol dm(-3), probably ion-paired by hydrogen bonds to the chloride ions. Mercury(ii) bromide also dissociates to ionic complexes in liquid ammonia and forms a homogeneous solution for which (199)Hg NMR indicates weak bromide association with mercury(ii). When dissolving mercury(ii) iodide in liquid ammonia and triethyl phosphite solvated molecular complexes form in the solutions. The Raman nu(I-Hg-I) symmetric stretching frequency is 132 cm(-1) for the pseudo-tetrahedral [HgI(2)(NH(3))(2)] complex formed in liquid ammonia, corresponding to D(S) = 56 on the donor strength scale. For the Hg(ClO(4))(2)/NH(4)I system in liquid ammonia a (199)Hg NMR study showed [HgI(4)](2-) to be the dominating mercury(ii) complex for mole ratios n(I(-)) : n(Hg(2+)) > or = 6. A large angle X-ray scattering (LAXS) study of mercury(ii) iodide in triethyl phosphite solution showed a [HgI(2)(P(OC(4)H(9))(3))(2)] complex with the Hg-I and Hg-P bond distances 2.750(3) and 2.457(4) A, respectively, in near tetrahedral configuration. Trialkylphosphines generally form very strong bonds to mercury(ii), dissociating all mercury(ii) halides. Mercury(ii) chloride and bromide form solid solvated mercury(ii) halide salts when treated with tri-n-butylphosphine, because of the low permittivity of the solvent. A LAXS study of a melt of mercury(ii) iodide in tri-n-butylphosphine at 330 K resulted in the Hg-I and Hg-P distances 2.851(3) and 2

  4. 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

  5. Structural properties and adsorption capacity of holocellulose aerogels synthesized from an alkali hydroxide-urea solution

    NASA Astrophysics Data System (ADS)

    Kwon, Gu-Joong; Kim, Dae-Young; Hwang, Jae-Hyun; Kang, Joo-Hyon

    2014-05-01

    A tulip tree was used to synthesize a holocellulose aerogel from an aqueous alkali hydroxide-urea solution with the substitution of an organic solvent followed by freeze-drying. For comparison, the synthesized holocellulose aerogels were divided into two groups according to the source of the hydrogel, an upper suspended layer and a bottom concentrated layer of the centrifuged solution of cellulose and NaOH/urea solvents. We investigated the effects of the temperature of the pre-cooled NaOH/urea solution ( i.e., dissolution temperature) on the pore structure and the adsorption capacity of the holocellulose aerogel. A nano-fibrillar network structure of the holocellulose aerogel was observed, with little morphological difference in pore structure for different dissolution temperatures. Both micropores and mesopores were observed in the holocellulose aerogel. The specific surface area of the holocellulose aerogel was generally greater at lower dissolution temperatures. In a series of adsorption tests using methylene blue, the holocellulose aerogel showed the greatest adsorption capacity at the lowest dissolution temperature tested (-2°C). However, the dissolution temperature generally had little effect on the adsorption capacity. The holocellulose aerogel produced from the upper suspended layer of the centrifuged hydrogel solution showed a greater porosity and adsorption capacity than the one produced from the bottom concentrated layer. Overall, the aerogel made by utilizing a delignified tulip tree display a high surface area and a high adsorption property, indicating its possible application in eco-friendly adsorption materials.

  6. Properties of alkali-solubilized collagen solution crosslinked by N-hydroxysuccinimide activated adipic acid

    NASA Astrophysics Data System (ADS)

    Chen, Yihui; Zhang, Min; Liu, Wentao; Li, Guoying

    2011-03-01

    The effect of N-hydroxysuccinimide activated adipic acid (NHS-AA) on the properties of alkali-solubilized collagen solutions was examined. The residual amino group content in crosslinked collagen, determined by trinitrobenzensulfonic acid (TNBS) assay, was decreased with increasing NHS-AA concentration. The results from differential scanning calorimeter (DSC) indicated that the maximum denaturation temperature ( T d) of crosslinked collagen solution was about 4.2°C higher than that of un-crosslinked collagen solution (36.6°C). Moreover, the values of storage modulus ( G'), loss modulus ( G″) and complex viscosity ( η*), obtained by means of dynamic frequency sweeps, were increased as NHS-AA concentration added up to 1.5 mM, and then decreased slightly when further increased NHS-AA concentration. Besides, for collagen solution crosslinked with 1.5 mM NHS-AA, dynamic denaturation temperature ( T dd) was about 1.1°C lower than T d (40.8°C), and the Arrhenius-type time-temperature superposition (TTS) principle was applied to yield the activation energy to be 474.4 kJmol-1.

  7. [Fluorescence enhancement of flavoxate hydrochloride in alkali solution and its application in pharmaceutical analysis].

    PubMed

    Li, Wen-hong; Sun, Chong-mei; Wei, Yong-ju

    2015-10-01

    Fluorescence enhancement reaction of flavoxate hydrochloride (FX) in strong alkali solution was studied, the mechanism of the reaction was investigated, and a novel fluorimetric method for analysis of FX in drug sample was established. FX has no intrinsic fluorescence, but it can slowly produce fluorescence in strong alkali solution. Heating can promote the fluorescence enhancement reaction. In 3D fluorescence spectra of the decomposition product of FX, two fluorescence peaks, located respectively at excitation wavelengths λex/ emission wavelength λem =223/410 nm, and 302/410 nm, were observed. Using quinine sulfate as a reference, fluorescence quantum yield of the decomposition product was measured to be 0.50. The structural characteriza- tion and spectral analysis of the decomposition product reveal that ester bond hydrolysis reaction of FX is firstly occurred during heating process, forming 3-methylflavone-8-carboxylic acid (MFA), then a cleavage reaction of the γ-pyrone ring of MFA occurred, producing α, β-unsaturated ketone. This product includes adjacent hydroxyl benzoic acid group in its molecule, which can form intramolecular hydrogen bond under alkaline condition, so that increase the conjugate degree and enhance the rigidity of the molecule, and thereby cause fluorescence enhancement. Based on this fluorescence enhancement reaction, a fluorimetric method was proposed for the determination of FX. A linear calibration curve covered the concentration range 0.020 3-0.487 µg · mL. The regression equation was I(F) = 23.9 + 5357.3 c, with correlation coefficient r = 0.999 7 (n = 8), detection limit D = 1.1 ng · mL(-1). The method was applied to the analysis of FX tablets, with a spiked recovery rate of 100.2%. The reliability of the method was verified by a UV-spectrophotometric method. PMID:26837181

  8. 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.

  9. Transparent cellulose films with high gas barrier properties fabricated from aqueous alkali/urea solutions.

    PubMed

    Yang, Quanling; Fukuzumi, Hayaka; Saito, Tsuguyuki; Isogai, Akira; Zhang, Lina

    2011-07-11

    Transparent and bendable regenerated cellulose films prepared from aqueous alkali (NaOH or LiOH)/urea (AU) solutions exhibit high oxygen barrier properties, which are superior to those of conventional cellophane, poly(vinylidene chloride), and poly(vinyl alcohol). Series of AU cellulose films are prepared from different cellulose sources (cotton linters, microcrystalline cellulose powder, and softwood bleached kraft pulp) for different dissolution and regeneration conditions. The oxygen permeabilities of these AU cellulose films vary widely from 0.003 to 0.03 mL μm m(-2) day(-1) kPa(-1) at 0% relative humidity depending on the conditions used to prepare the films. The lowest oxygen permeability is achieved for the AU film prepared from 6 wt % cellulose solution by regeneration with acetone at 0 °C. The oxygen permeabilities of the AU cellulose films are negatively correlated with their densities, and AU films prepared from solutions with high cellulose concentrations by regeneration in a solvent at low temperatures generally have low oxygen permeabilities. The AU cellulose films are, therefore, promising biobased packaging materials with high-oxygen barrier properties. PMID:21657790

  10. 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

  11. Structures of the 2-nitrophenol alkali complexes in solution and the solid state

    NASA Astrophysics Data System (ADS)

    Reichelt, Hendrik; Faunce, Chester A.; Paradies, Henrich H.

    2015-07-01

    The materials studied in this investigation were aqueous solutions (0.02-25.0 mM) of the salts of alkali metal ion (Me+) and 2-nitrophenol (2-NP). In the investigation, small-angle X-ray scattering, wide-angle X-ray scattering, and membrane-pressure osmometry were used to study the 2-NP-Me+ molecular salt structures and the onset of crystallization as a function of concentration and temperature. The experimental methods used to examine the 2-NP-Me+ molecular salt complexes provided corroborative evidence for the existence of spherical clusters with hydrodynamic diameters between ˜12 Å (Li) and 14 Å (Cs). Guinier plots of the zero-angle scattering peak were characteristic of the scattering from lamellae-like shapes with thicknesses of ˜290 Å. Tetramer and pentamer 2-NP-Me+ molecular clusters for Me+ = Li, Na, K, and Rb were assembled from four or five 2-NP molecules bound to a central alkali metal ion. The coordination symmetry around the six coordinated Li+, Na+, and K+ ions was that of a trigonal prism (D3h), with an octahedral arrangement (D2h). The Rb+ also revealed six-coordinate geometry and the central Rb+ ion adopted an octahedral arrangement (D2h). The eight-coordinated Cs+ ions with six 2-NP ligands were characteristic of a square antiprism (D4d). The square antiprism was the outcome of leaving two o-nitro groups and two phenolic oxygens being left intermolecularly uncoordinated to the Cs+ ion. The 2-NP residues were strictly planar and contained short non-bonded intramolecular distances. van der Waals forces were present between the adjacently stacked phenyl rings. No water molecules were involved as ligands for any of the 2-nitrophenol-Me+ complexes.

  12. The C-I···X¯ halogen bonding of tetraiodoethylene with halide anions in solution and cocrystals investigated by experiment and calculation.

    PubMed

    Wang, Hui; Zhao, Xiao Ran; Jin, Wei Jun

    2013-03-28

    The selection of the halogen bonding (XB) donor is an important factor in molecular recognition of halides by XB. Here XB complexes between tetraiodoethylene (TIE) as another donor instead of iodoperfluorobenzene and halides are investigated using UV-Vis, Raman, FT-IR, XRD, PXRD and calculations. A 1 : 1 stoichiometry of TIE with halide anions in dilute solution is confirmed. Comparatively, the TIECl(-) complex possesses greater bonding constant and molar extinction coefficient than TIEBr(-)/I(-), probably due to Cl(-) having the most negative electrostatic potential, or higher electronic density due to its small size. The XRD reveals that TIE/Cl(-) and TIE/I(-) cocrystals always keep the stoichiometry of 3 : 1 and 1 : 1, respectively, regardless of which solvent is used for preparing them. But the intermediate TIE/Br(-) cocrystals swing between 3 : 1 and 1 : 1. These results indicate that the TIEBr(-) complex should be influenced more easily by solvent nature and the stoichiometries of interaction between TIE and halide anions are different in solution and cocrystals. Moreover, the calculation of energies of XB interaction indicates that the XB strength of C-IX(-) is much stronger in the gas-phase and cocrystals than in solution, and much stronger than C-Iπ and C-II-C contacts in cocrystals. The study will be of benefit in anion recognition and new material design using XB. PMID:23407673

  13. Washing of Petroleum and Arsenic Contaminated Soil with Ultrasound and Alkali Phosphate Solution

    NASA Astrophysics Data System (ADS)

    Lee, Jung Hwa; Kim, Jae Gon; Cho, Yong-chan; Chon, Chul-Min; Nam, In-Hyun; Keum, Mi Jung

    2015-04-01

    Soil washing of fine textured soil has been a challenging remedial strategy due to its low remediation efficiency. We adapted ultrasound and dispersion solution to increase the remediation efficiency of the soil washing. The ultrasound and dispersion agent may enhance the dispersion of the aggregate into individual particles and may enhance release of contaminants from the aggregate. We collected the arsenic (As) contaminated silt loam soil from a smelting site, spiked with 1% of diesel and incubated for 6 months. We tested the dispersion rate and the release of diesel with the incubated soil at various pH and concentrations of orthophosphate, pyrophosphate and hexametaphosphate with or without the ultrasound of 28 kHz and 400 W. The As concentrations of coarse (> medium silt) and fine (solution. The application of ultrasound sharply increased the dispersion rate and diesel release comparing with no ultrasound. The optimum condition of the soil washing was turned out to be pH 11_10 mM Na-hexametaphosphate with the ultrasound. The concentration of total petroleum hydrocarbon of the incubated soil reduced from 3101.3 mg kg-1 to 14.0 mg kg-1 after 10 minute washing at the optimum condition. The fine fraction had much higher As concentration than the coarse fraction: 44.4 mg kg-1 for the fine fraction and 14.4 mg kg-1 for the coarse fraction. The results of this study indicate that the ultrasound and alkali phosphate solution increase the soil washing efficiency and can be a promising technology for the remediation of fine textured contaminated soils. Key Words : Ultrasound, Phosphate solution, Soil washing, Mixed contaminants

  14. Kinetics of aggregation and growth processes of PEG-stabilised mono- and multivalent gold nanoparticles in highly concentrated halide solutions.

    PubMed

    Stein, Benjamin; Zopes, David; Schmudde, Madlen; Schneider, Ralf; Mohsen, Ahmed; Goroncy, Christian; Mathur, Sanjay; Graf, Christina

    2015-01-01

    5-6 nm gold nanoparticles were prepared by hydrolytic decomposition of [NMe4][Au(CF3)2] and functionalized in situ with mono- and multivalent thiolated PEG ligands. Time-dependent changes of the nanoparticles were monitored in aqueous NaCl, NaBr, and NaI solutions by UV-Vis spectroscopy, TEM, and HRTEM. The purely sterically protected particles are stable in ≤1 M NaCl and NaBr solutions, regardless of the valence of the ligands. At higher concentrations (≥2 M), the monovalent stabilized particles show minor reaction limited colloidal aggregation. In NaBr but not in NaCl solutions a minor Ostwald ripening also occurs. The divalent stabilized particles remain colloidally stable in both halide solutions, even if the temperature is raised or the concentration is increased above 2 M. In ≤1 M aqueous NaI solutions the particles remain stable. Above, the monovalent stabilized particles undergo an oxidative reaction, resulting in a time-dependent shift and broadening of the absorbance spectrum. Finally, this process slows down while the width of the spectra slightly narrows. The kinetics of this process can be described by a two-step sigmoidal process, comprising a slow induction period where active species are formed, followed by a fast growth and aggregation process. The increasing concentration of fused structures from the aggregates during this process results in a narrowing of the size distributions. The divalent stabilized particles show only some minor broadening and a slight shift of the absorbance spectra in ≤3 M NaI solutions. These observations confirm the excellent stability of the multivalent stabilized particles from this chloride-free particle synthesis. PMID:25972038

  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. The molecular velocity of sound. [aqueous solutions

    NASA Technical Reports Server (NTRS)

    Auslaender, D.; Onitiu, L.

    1974-01-01

    The molecular velocity of sound was calculated according to Rao's formula and the temperature and concentration dependences of this value were studied in aqueous solutions of alkali and alkaline-earth halides. Study of relative association brought to light characteristic effects of ions. The variation of the relative association can be explained by a breaking of hydrogen bonds by ions and thermal agitation.

  17. X-ray photoelectron spectroscopy of fast-frozen hematite colloids in aqueous solutions. 5. Halide ion (F-, Cl-, Br-, I-) adsorption.

    PubMed

    Shimizu, Kenichi; Shchukarev, Andrey; Kozin, Philipp A; Boily, Jean-François

    2013-02-26

    Halide anion (F(-), Cl(-), Br(-), and I(-)) adsorption and its impact on sodium adsorption at the hematite/water interface were studied by cryogenic X-ray photoelectron spectroscopy (XPS). Measurements were carried out on frozen, centrifuged wet hematite pastes that were previously equilibrated in 50 mM electrolytic solutions in the pH 2-11 range. XPS-derived halide ion surface loadings decreased in the order F(-) > I(-) ≈ Cl(-) > Br(-), whereas sodium loadings were in the order Na(F) > Na(I) > Na(Br) > Na(Cl). The greater sodium loadings in NaF and in NaI resulted from larger anion loadings in these systems. Bromide ion had the lowest loading among all halide ions despite having a charge-to-size ratio that is intermediate between those of Cl(-) and I(-). This unexpected result may have arisen from specific properties of the hematite/water interface, such as water structure and electric double layer thickness. Fluoride ion adsorption proceeded via the formation of hydrogen bonds with the surface hydroxo groups (e.g., ≡Fe-OH(2)···F(-) or ≡Fe-OH···F(-)). Surface-bound fluoride ions exert a greater charge-screening effect than the other halide anions, as demonstrated by considerably small zeta potential values. Fe-F bond formation was excluded as a possible interfacial process as the F 1s peak binding energy (684.2 eV) was more comparable to that of NaF (684.6 eV) than FeF(3) (685.4 eV). Overall, these findings motivate further refinements of existing thermodynamic adsorption models for predicting the ionic composition of hematite particle surfaces contacted with sodium halide aqueous solutions. PMID:23347248

  18. Adsorption of halide ions from aqueous solutions at a Cd(0 0 0 1) electrode surface: quantum chemical modelling and experimental study

    NASA Astrophysics Data System (ADS)

    Nazmutdinov, Renat R.; Zinkicheva, Tamara T.; Probst, Michael; Lust, Karmen; Lust, Enn

    2005-03-01

    Adsorption of the halide ions X (X = Cl -, Br -, I -) at a cadmium monocrystalline face (0 0 0 1) from aqueous solutions has been studied by the impedance spectroscopy. Analysis of the impedance data does not predict specific adsorption for Cl - and shows that the Gibbs adsorption energy increases from Br - to I - in accordance with the decrease of the hydration energy of anions. The adsorption of halide ions and their atomic forms on a Cd(0 0 0 1) electrode at the potential of zero charge (pzc) has been studied with the use of the cluster model. The quantum chemical calculations were performed at the DFT and the SCF levels involving the hydrated species X -(H 2O) 3 and X -(H 2O) 6 besides the bare anions. The effective distance-dependent solvation energy of halide ions constructed on the basis of molecular dynamics simulations was used to build the adsorption terms. For all three halides contact adsorption was found to be the most favourable state. The partial charge transfer (PCT) from the adsorbed species to the metal was analysed in terms of the Anderson-Newns model. A combined consideration of the solvation and PCT effects enables prediction of the experimentally observed metal-ion interaction order (Cl - < Br - < I -).

  19. 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.

  20. Adsorption of halide anions at the Pt(111)-solution interfacestudied by in situ surface x-ray scattering

    NASA Astrophysics Data System (ADS)

    Lucas, C. A.; Marković, N. M.; Ross, P. N.

    1997-03-01

    In this paper we present x-ray scattering results of iodide, bromide, and chloride adsorption onto the Pt(111) surface in solution. Iodide forms two commensurate adlayer structures, a (7×7)R19.1° phase and a hexagonal (3×3) phase, which coexist on the Pt surface. Formation of the (3×3) phase appears to be kinetically limited, whereas the 7 phase shows a hysteretic effect as a function of the electrode potential, associated with an order-disorder transition. Bromide forms a series of high-order commensurate structures on Pt(111) that are poorly ordered unless the size of the unit cell is small. No ordered structures for chloride adsorption are observed and specular x-ray reflectivity results suggest that the chloride coverage at low potential is too small to form a close-packed monolayer on the surface. The differences between the structures formed by the adsorbed anions, and the differences between results for Pt(111) and Au(111), are discussed in terms of the strength of the metal-halide interaction.

  1. Detection of X-ray photons by solution-processed lead halide perovskites

    NASA Astrophysics Data System (ADS)

    Yakunin, Sergii; Sytnyk, Mykhailo; Kriegner, Dominik; Shrestha, Shreetu; Richter, Moses; Matt, Gebhard J.; Azimi, Hamed; Brabec, Christoph J.; Stangl, Julian; Kovalenko, Maksym V.; Heiss, Wolfgang

    2015-07-01

    The evolution of real-time medical diagnostic tools such as angiography and computer tomography from radiography based on photographic plates was enabled by the development of integrated solid-state X-ray photon detectors made from conventional solid-state semiconductors. Recently, for optoelectronic devices operating in the visible and near-infrared spectral regions, solution-processed organic and inorganic semiconductors have also attracted a great deal of attention. Here, we demonstrate a possibility to use such inexpensive semiconductors for the sensitive detection of X-ray photons by direct photon-to-current conversion. In particular, methylammonium lead iodide perovskite (CH3NH3PbI3) offers a compelling combination of fast photoresponse and a high absorption cross-section for X-rays, owing to the heavy Pb and I atoms. Solution-processed photodiodes as well as photoconductors are presented, exhibiting high values of X-ray sensitivity (up to 25 μC mGyair-1 cm-3) and responsivity (1.9 × 104 carriers/photon), which are commensurate with those obtained by the current solid-state technology.

  2. Effects of topical 10% ascorbate solution on established corneal ulcers after severe alkali burns.

    PubMed

    Pfister, R R; Paterson, C A; Hayes, S A

    1982-03-01

    When established corneal ulcers induced by alkali burning were treated with 10% ascorbate drops, no perforation occurred, in contrast to a 25% incidence in the control group. If perforations and descemetoceles were grouped together, these difference became insignificant (i.e., 14.2% ascorbate-treated vs. 25% control). Prolongation of descemetocele presence without perforation in the ascorbate-treated group indicated some therapeutic effect. We conclude that topical ascorbate does not substantially alter the outcome of established corneal ulcers. PMID:7061209

  3. Antimony porphyrins as red-light powered photocatalysts for solar fuel production from halide solutions in the presence of air.

    PubMed

    Ertl, M; Wöß, E; Knör, G

    2015-10-01

    Halide ions (X(-)) as cheap and abundant electron donors are oxidized with simulated sunlight in a photocatalytic reaction based on robust antimony porphyrins acting as red-light harvesting multielectron transfer sensitizers. Besides halogen formation (X2/X3(-)) this solar energy storing process under certain conditions also accumulates hydrogen peroxide (H2O2) as a second energy-rich compound. PMID:26360604

  4. Water adsorption, solvation and deliquescence of alkali halide thin films on SiO2 studied by ambient pressure X-ray photoelectron spectroscopy

    SciTech Connect

    Arima, Kenta; Jiang, Peng; Deng, Xingyi; Bluhm, Henrik; Salmeron, Miquel

    2010-03-31

    The adsorption of water on KBr thin films evaporated onto SiO2 was investigated as a function of relative humidity (RH) by ambient pressure X-ray photoelectron spectroscopy. At 30percent RH adsorbed water reaches a coverage of approximately one monolayer. As the humidity continues to increase, the coverage of water remains constant or increases very slowly until 60percent RH, followed by a rapid increase up to 100percent RH. At low RH a significant number of the Br atoms are lost due to irradiation damage. With increasing humidity solvation increases ion mobility and gives rise to a partial recovery of the Br/K ratio. Above 60percent RH the increase of the Br/K ratio accelerates. Above the deliquescence point (85percent RH), the thickness of the water layer continues to increase and reaches more than three layers near saturation. The enhancement of the Br/K ratio at this stage is roughly a factor 2.3 on a 0.5 nm KBr film, indicating a strong preferential segregation of Br ions to the surface of the thin saline solution on SiO2.

  5. A facile one-step solution deposition via non-solvent/solvent mixture for efficient organometal halide perovskite light-emitting diodes.

    PubMed

    Jiao, Bo; Zhu, Xiaobo; Wu, Wen; Dong, Hua; Xia, Bin; Xi, Jun; Lei, Ting; Hou, Xun; Wu, Zhaoxin

    2016-06-01

    Although organometal halide perovskite materials have shown great potential in light-emitting diodes, their performance is greatly restricted by the poor morphology of the perovskite layer. In this work, we demonstrate a facile one-step solution method to improve the perovskite film morphology via a non-solvent/solvent mixture. An efficient CH3NH3PbBr3-based light-emitting diode was prepared with a chlorobenzene/N,N-dimethylformamide mixed solvent. A high efficiency of 0.54 cd A(-1) is demonstrated, which is 22 times higher than that of a device fabricated by a traditional one-step solution process. Furthermore, the uniformity of the emission region and the device stability are strongly improved by this facile one-step solution process. Our work paves a new way for the morphological control of perovskite films for application in light-emitting diodes. PMID:27227355

  6. A facile one-step solution deposition via non-solvent/solvent mixture for efficient organometal halide perovskite light-emitting diodes

    NASA Astrophysics Data System (ADS)

    Jiao, Bo; Zhu, Xiaobo; Wu, Wen; Dong, Hua; Xia, Bin; Xi, Jun; Lei, Ting; Hou, Xun; Wu, Zhaoxin

    2016-05-01

    Although organometal halide perovskite materials have shown great potential in light-emitting diodes, their performance is greatly restricted by the poor morphology of the perovskite layer. In this work, we demonstrate a facile one-step solution method to improve the perovskite film morphology via a non-solvent/solvent mixture. An efficient CH3NH3PbBr3-based light-emitting diode was prepared with a chlorobenzene/N,N-dimethylformamide mixed solvent. A high efficiency of 0.54 cd A-1 is demonstrated, which is 22 times higher than that of a device fabricated by a traditional one-step solution process. Furthermore, the uniformity of the emission region and the device stability are strongly improved by this facile one-step solution process. Our work paves a new way for the morphological control of perovskite films for application in light-emitting diodes.Although organometal halide perovskite materials have shown great potential in light-emitting diodes, their performance is greatly restricted by the poor morphology of the perovskite layer. In this work, we demonstrate a facile one-step solution method to improve the perovskite film morphology via a non-solvent/solvent mixture. An efficient CH3NH3PbBr3-based light-emitting diode was prepared with a chlorobenzene/N,N-dimethylformamide mixed solvent. A high efficiency of 0.54 cd A-1 is demonstrated, which is 22 times higher than that of a device fabricated by a traditional one-step solution process. Furthermore, the uniformity of the emission region and the device stability are strongly improved by this facile one-step solution process. Our work paves a new way for the morphological control of perovskite films for application in light-emitting diodes. Electronic supplementary information (ESI) available: MABr/PbBr ratio optimization, film thickness and AFM morphology. See DOI: 10.1039/c6nr01092j

  7. Bioactive surface modification of Ti-29Nb-13Ta-4.6Zr alloy through alkali solution treatments.

    PubMed

    Takematsu, E; Katsumata, K; Okada, K; Niinomi, M; Matsushita, N

    2016-05-01

    Bioactive surface modification of Ti-29Nb-13Ta-4.6Zr alloy (TNTZ) was performed through three different alkali solution treatments, including the electrochemical (E), hydrothermal (H), and hydrothermal-electrochemical (HE) processes; all of the processes lead to the formation of sodium-contained amorphous titanium oxide layers on TNTZ samples. The TNTZ samples subjected to the E, H, and HE processes exhibit a flat surface, smooth and fine mesh-like structure surface, and rough mesh-like structure surface, respectively. In the bioactive test, namely, simulated body fluid test, apatite inductivity increases as the surface morphology becomes rough. The order of inductivity for the three processes was HE>H>E. The surface chemical composition also affects the apatite induction ability. The surface with fewer niobium species exhibits better apatite inductivity. PMID:26952470

  8. Adhesive strength of bioactive oxide layers fabricated on TNTZ alloy by three different alkali-solution treatments.

    PubMed

    Takematsu, E; Cho, K; Hieda, J; Nakai, M; Katsumata, K; Okada, K; Niinomi, M; Matsushita, N

    2016-08-01

    Bioactive oxide layers were fabricated on Ti-29Nb-13Ta-4.6Zr alloy (TNTZ) by three different alkali solution treatments: hydrothermal (H), electrochemical (E), and hydrothermal-electrochemical (HE). The adhesive strength of the oxide layer to the TNTZ substrate was measured to determine whether this process achieves sufficient adhesive strength for implant materials. Samples subjected to the HE process, in which a current of 15mA/cm(2) was applied at 90°C for 1h (HE90-1h), exhibited a comparatively higher adhesive strength of approximately 18MPa while still maintaining a sufficiently high bioactivity. Based on these results, an oxide layer fabricated on TNTZ by HE90-1h is considered appropriate for practical biomaterial application, though thicker oxide layers with many cracks can lead to a reduced adhesive strength. PMID:26866453

  9. Solution-Derived, Chloride-Containing Minerals as a Waste Form for Alkali Chlorides

    SciTech Connect

    Riley, Brian J.; Crum, Jarrod V.; Matyas, Josef; McCloy, John S.; Lepry, William C.

    2012-10-01

    Sodalite [Na8(AlSiO4)6Cl2] and cancrinite [(Na,K)6Ca2Al6Si6O24Cl4] are environmentally stable, chloride-containing minerals and are a logical waste form option for the mixed alkali chloride salt waste stream that is generated from a proposed electrochemical separations process during nuclear fuel reprocessing. Due to the volatility of chloride salts at moderate temperatures, the ideal processing route for these salts is a low-temperature approach such as the sol-gel process. The sodalite structure can be easily synthesized by the sol-gel process; however, it is produced in the form of a fine powder with particle sizes on the order of 1–10 µm. Due to the small particle size, these powders require additional treatment to form a monolith. In this study, the sol-gel powders were pressed into pellets and fired to achieve > 90% of theoretical density. The cancrinite structure, identified as the best candidate mineral form in terms of waste loading capacity, was only produced on a limited basis following the sol-gel process and converted to sodalite upon firing. Here we discuss the sol-gel process specifics, chemical durability of select waste forms, and the steps taken to maximize chloride-containing phases, decrease chloride loss during pellet firing, and increase pellet densities.

  10. 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.

  11. 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.

  12. X-ray and neutron scattering studies of the hydration structure of alkali ions in concentrated aqueous solutions.

    PubMed

    Ansell, S; Barnes, A C; Mason, P E; Neilson, G W; Ramos, S

    2006-12-01

    The presence of ions in water provides a rich and varied environment in which many natural processes occur with important consequences in biology, geology and chemistry. This article will focus on the structural properties of ions in water and it will be shown how the 'difference' methods of neutron diffraction with isotopic substitution (NDIS) and anomalous X-ray diffraction (AXD) can be used to obtain direct information regarding the radial pair distribution functions of many cations and anions in solution. This information can subsequently be used to calculate coordination numbers and to determine ion-water conformation in great detail. As well as enabling comparisons to be made amongst ions in particular groups in the periodic table, such information can also be contrasted with results provided by molecular dynamics (MD) simulation techniques. To illustrate the power of these 'difference' methods, reference will be made to the alkali group of ions, all of which have been successfully investigated by the above methods, with the exception of the radioactive element francium. Additional comments will be made on how NDIS measurements are currently being combined with MD simulations to determine the structure around complex ions and molecules, many of which are common in biological systems. PMID:16815625

  13. Sulfate Separation from Aqueous Alkaline Solutions by Selective Crystallization of Alkali Metal Coordination Capsules

    SciTech Connect

    Rajbanshi, Arbin; Moyer, Bruce A; Custelcean, Radu

    2011-01-01

    Self-assembly of a tris(urea) anion receptor with Na{sub 2}SO{sub 4} or K{sub 2}SO{sub 4} yields crystalline capsules held together by coordinating Na{sup +} or K{sup +} cations and hydrogen-bonding water bridges, with the sulfate anions encapsulated inside urea-lined cavities. The sodium-based capsules can be selectively crystallized in excellent yield from highly competitive aqueous alkaline solutions ({approx}6 M Na{sup +}, pH 14), thereby providing for the first time a viable approach to sulfate separation from nuclear wastes.

  14. Alkali metal Rankine cycle boiler technology challenges and some potential solutions for space nuclear power and propulsion applications

    NASA Astrophysics Data System (ADS)

    Stone, James R.

    1994-07-01

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

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

    NASA Technical Reports Server (NTRS)

    Stone, James R.

    1994-01-01

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

  16. Alkali modified hydrochar of grape pomace as a perspective adsorbent of Pb(2+) from aqueous solution.

    PubMed

    Petrović, Jelena T; Stojanović, Mirjana D; Milojković, Jelena V; Petrović, Marija S; Šoštarić, Tatjana D; Laušević, Mila D; Mihajlović, Marija L

    2016-11-01

    Hydrochar produced via hydrothermal carbonization of grape pomace was considered as novel sorbent of Pb(2+) from aqueous solution. In order to enhance the adsorption capacity, hydrochar was chemically modified using 2 M KOH solution. Both materials were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy and X-ray diffraction technique. Batch experiments were performed to examine the effect of sorbent dosage, pH and contact time. Obtained results showed that the KOH treatment increased the sorption capacity of hydrochar from 27.8 mg g(-1) up to 137 mg g(-1) at pH 5. Adsorption of lead on either of the materials was achieved through ion-exchange mechanism, chemisorption and Pb(2+)-π interaction. The Sips isotherm model gave the best fit with the experimental data obtained for Pb(2+) sorption using activated hydrochar. The adsorption kinetic followed a pseudo second-order model. Thermodynamic parameters implied that the Pb(2+) binding for hydrochar surface was spontaneous and exothermic process. Findings from this work suggest that the hydrothermal carbonization is a promising route for production of efficient Pb (2+) sorbents for wastewater treatment. PMID:27494605

  17. Removal of mercury(II) from aqueous solutions and chlor-alkali industry wastewater using 2-mercaptobenzimidazole-clay.

    PubMed

    Manohar, D M; Krishnan, K Anoop; Anirudhan, T S

    2002-03-01

    The 2-mercaptobenzimidazole loaded natural clay was prepared for the removal of Hg(II) from aqueous media. Adsorption of the metal ions from aqueous solution as a function of solution concentration, agitation time, pH, temperature, ionic strength, particle size of the adsorbent and adsorbent dose was studied. The adsorption process follows a pseudo-second-order kinetics. The rate constants as a function of initial concentration and temperature were given. The adsorption of Hg(II) increased with increasing pH and reached a plateau value in the pH range 4.0-8.0. The removal of Hg(II) was found to be >99% at an initial concentration of 50 mg/l. Mercury(II) uptake was found to increase with ionic strength and temperature. Further, the adsorption of Hg(II) increased with increasing adsorbent dose and decrease with adsorbent particle size. Sorption data analysis was carried out using Langmuir and modified Langmuir isotherms for the uptake of metal ion in an initial concentration range of 50-1,000 mg/l. The significance of the two linear relationships obtained by plotting the data according to the conventional Langmuir equation is discussed in terms of the binding energies of the two population sites involved which have a widely differing affinity for Hg(II) ions. Thermodynamic parameters such as changes of free energy, enthalpy, and entropy were calculated to predict the nature of adsorption. It was found that the values of isosteric heat of adsorption were varied with surface loading. The chlor-alkali industry wastewater samples were treated by MBI-clay to demonstrate its efficiency in removing Hg(II) from wastewater. PMID:11996349

  18. Stability constants and thermodynamic data for complexes of 12-crown-4 with alkali metal and alkaline-earth cations in methanol solutions

    SciTech Connect

    Buschmann, H.

    1987-03-01

    The formation of 1:1- and 2:1-complexes of the crown ether 12C4 with mono- and bivalent cations was studied in methanol solutions by calorimetric, potentiometric and conductometric titrations. It is shown that not all donor atoms of the ligand 12C4 take part in complex formation. The accuracy of the three experimental methods are checked by comparing the results for the complexation of alkali ions with crown ether 18C6.

  19. 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)

  20. Light Emission from Porous Silicon Photoetched in Aqueous Alkali Salt Solutions

    NASA Astrophysics Data System (ADS)

    Adachi, Sadao; Miyazaki, Takayuki; Inoue, Kazufumi; Sodezawa, Shingo

    2007-07-01

    An interband-transition model was applied to explain the emission mechanism in porous silicon (PSi) fabricated by photoetching in aqueous HF and salt (NaF and KF) solutions. The HF-formed samples show a yellow photoluminescence band at ˜2 eV. The salt-formed samples, on the other hand, show an ultraviolet (UV) emission peak at ˜3.3 eV with a spectral width of ˜0.1 eV, together with a broad emission band at ˜2.7 eV. The broad emission bands at ˜2 and ˜2.7 eV can be explained by the quantum-mechanical confinement effect, i.e., a relaxation of the momentum conservation at and above the indirect-absorption edge (supra-EgID emission). This effect may also lead to a change in the E1 critical point (CP) from the two-dimensional M0 to the zero-dimensional CP with decreasing nanocrystalline size. The change in the E1-CP dimensionality makes possible an emission in the UV region with a narrow spectral width.

  1. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  3. Nuclear magnetic resonance studies of supercooled aqueous electrolyte solutions

    NASA Astrophysics Data System (ADS)

    Lang, E. W.; Bradl, S.; Fink, W.; Radkowitsch, H.; Girlich, D.

    1990-12-01

    The dynamic properties of water molecules coordinated to simple ions (alkali and alkali-earth halides) and hydrophobic ions (tetraalkylammonium (TAA) halides) in supercooled solutions have been investigated with NMR. The study of spin-lattice relaxation rates and self-diffusion coefficients as functions of temperature, pressure Larmor frequency and concentration reveals characteristic features of molecular motions close to the low-temperature limit of the metastable phase (percolation transition and glass transition) and provides certain details of the local arrangement of water molecules in the coordination sphere of these ions. The intramolecular flexibility of the alkyl chains of the hydrated TAA cations has been investigated also. The dynamics of the methyl group reorientation provide a sensitive probe of structural differences in these solutions.

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

    NASA Astrophysics Data System (ADS)

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

    2003-12-01

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

  5. 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.

  6. Thermodynamic quantities of surface formation of aqueous electrolyte solutions. VI. Comparison with typical nonelectrolytes, sucrose and glucose.

    PubMed

    Matubayasi, Norihiro; Nishiyama, Ai

    2006-06-15

    To demonstrate an important distinction between the electrolytes and nonelectrolytes, surface tension of aqueous solutions of typical nonelectrolytes, sucrose and glucose, was measured as a function of temperature and concentration. The presence of sucrose or glucose molecules in the surface region affects the surface tension in the same way as the presence of an ion does. There is, however, a difference in the temperature coefficient of the surface tension between typical nonelectrolyte solutions, sucrose and glucose, and alkali halide solutions. The entropy of surface formation of sucrose and glucose solutions is the same as that of pure water, while that of alkali halide solutions decreases with concentration. The relation between this entropy change and the formation of electric double layers was discussed. PMID:16469326

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

    NASA Astrophysics Data System (ADS)

    Ashour, Rakan F.

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

  8. Zero-dipole molecular organic cations in mixed organic-inorganic halide perovskites: possible chemical solution for the reported anomalous hysteresis in the current-voltage curve measurements

    NASA Astrophysics Data System (ADS)

    Giorgi, Giacomo; Yamashita, Koichi

    2015-11-01

    Starting from a brief description of the main architectures characterizing the novel solar technology of perovskite-based solar cells, we focus our attention on the anomalous hysteresis experimentally found to affect the measurement of the current-voltage curve of such devices. This detrimental effect, associated with slow dynamic reorganization processes, depends on several parameters; among them, the scan rate of the measurements, the architecture of the cell, and the perovskite deposition rate are crucial. Even if a conclusive explanation of the origin of the hysteresis has not been provided so far, several experimental findings ascribe its origin to ionic migration at an applied bias and dielectric polarization that occurs in the perovskite layer. Consistently, a dipole-moment-reduced cation such as formamidinium ion is experimentally reported to quantitatively reduce the hysteresis from perovskite-based devices. By means of a density-functional theory-based set of calculations, we have predicted and characterized guanidinium ion (GA = +[C(NH2)3], a zero-dipole moment cation by symmetry)-based organic-inorganic halide perovskite’s structural and electronic properties, speculating that such a cation and the alloys it may form with other organic cations can represent a possible chemical solution for the puzzling issue of the hysteresis.

  9. Zero-dipole molecular organic cations in mixed organic-inorganic halide perovskites: possible chemical solution for the reported anomalous hysteresis in the current-voltage curve measurements.

    PubMed

    Giorgi, Giacomo; Yamashita, Koichi

    2015-11-01

    Starting from a brief description of the main architectures characterizing the novel solar technology of perovskite-based solar cells, we focus our attention on the anomalous hysteresis experimentally found to affect the measurement of the current-voltage curve of such devices. This detrimental effect, associated with slow dynamic reorganization processes, depends on several parameters; among them, the scan rate of the measurements, the architecture of the cell, and the perovskite deposition rate are crucial. Even if a conclusive explanation of the origin of the hysteresis has not been provided so far, several experimental findings ascribe its origin to ionic migration at an applied bias and dielectric polarization that occurs in the perovskite layer. Consistently, a dipole-moment-reduced cation such as formamidinium ion is experimentally reported to quantitatively reduce the hysteresis from perovskite-based devices. By means of a density-functional theory-based set of calculations, we have predicted and characterized guanidinium ion (GA = (+)[C(NH2)3], a zero-dipole moment cation by symmetry)-based organic-inorganic halide perovskite's structural and electronic properties, speculating that such a cation and the alloys it may form with other organic cations can represent a possible chemical solution for the puzzling issue of the hysteresis. PMID:26468971

  10. Dissecting ion-specific dielectric spectra of sodium-halide solutions into solvation water and ionic contributions

    SciTech Connect

    Rinne, Klaus F.; Netz, Roland R.; Gekle, Stephan

    2014-12-07

    Using extensive equilibrium molecular dynamics simulations we determine the dielectric spectra of aqueous solutions of NaF, NaCl, NaBr, and NaI. The ion-specific and concentration-dependent shifts of the static dielectric constants and the dielectric relaxation times match experimental results very well, which serves as a validation of the classical and non-polarizable ionic force fields used. The purely ionic contribution to the dielectric response is negligible, but determines the conductivity of the salt solutions. The ion-water cross correlation contribution is negative and reduces the total dielectric response by about 5%-10% for 1 M solutions. The dominating water dielectric response is decomposed into different water solvation shells and ion-pair configurations, by this the spectral blue shift and the dielectric decrement of salt solutions with increasing salt concentration is demonstrated to be primarily caused by first-solvation shell water. With rising salt concentration the simulated spectra show more pronounced deviations from a single-Debye form and can be well described by a Cole-Cole fit, in quantitative agreement with experiments. Our spectral decomposition into ionic and different water solvation shell contributions does not render the individual contributions more Debye-like, this suggests the non-Debye-like character of the dielectric spectra of salt solutions not to be due to the superposition of different elementary relaxation processes with different relaxation times. Rather, the non-Debye-like character is likely to be an inherent spectral signature of solvation water around ions.

  11. Optimum conditions to prepare high yield, phase pure α-Ni(OH) 2 nanoparticles by urea hydrolysis and electrochemical ageing in alkali solutions

    NASA Astrophysics Data System (ADS)

    Jayalakshmi, M.; Venugopal, N.; Reddy, B. Ramachandra; Rao, M. Mohan

    Phase pure alpha nickel hydroxide (α-Ni(OH) 2) is synthesized by a hydrothermal method using urea and nickel nitrate in an autoclave. Optimum conditions to obtain high yield and phase pure α-Ni(OH) 2 are identified by varying experimental parameters such as urea concentration, ramp time, and temperature. In a typical experiment, a 94% yield of phase pure α-Ni(OH) 2 is successfully prepared. The nickel content, analyzed by means of atomic absorption spectroscopy, is 44% in all samples. The α-Ni(OH) 2 nanoparticles are characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The BET surface area and tap density of the nickel hydroxide nanoparticles are also determined. Electrochemical characterization is undertaken via cyclic voltammetry for which the nanoparticles are immobilized on the surface of paraffin impregnated graphite electrodes in 1.0 M alkali solutions. The ageing of the alpha phase occurs within 27 min (30 cycles) of exposure in alkali solutions.

  12. 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.

  13. All solution-processed lead halide perovskite-BiVO4 tandem assembly for photolytic solar fuels production.

    PubMed

    Chen, Yong-Siou; Manser, Joseph S; Kamat, Prashant V

    2015-01-21

    The quest for economic, large-scale hydrogen production has motivated the search for new materials and device designs capable of splitting water using only energy from the sun. Here we introduce an all solution-processed tandem water splitting assembly composed of a BiVO4 photoanode and a single-junction CH3NH3PbI3 hybrid perovskite solar cell. This unique configuration allows efficient solar photon management, with the metal oxide photoanode selectively harvesting high energy visible photons, and the underlying perovskite solar cell capturing lower energy visible-near IR wavelengths in a single-pass excitation. Operating without external bias under standard AM 1.5G illumination, the photoanode-photovoltaic architecture, in conjunction with an earth-abundant cobalt phosphate catalyst, exhibits a solar-to-hydrogen conversion efficiency of 2.5% at neutral pH. The design of low-cost tandem water splitting assemblies employing single-junction hybrid perovskite materials establishes a potentially promising new frontier for solar water splitting research. PMID:25543877

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

    PubMed

    Crea, Francesco; De Stefano, Concetta; Foti, Claudia; Lando, Gabriele; Milea, Demetrio; Sammartano, Silvio

    2016-01-01

    Alkali metal ions play very important roles in all biological systems, some of them are essential for life. Their concentration depends on several physiological factors and is very variable. For example, sodium concentrations in human fluids vary from quite low (e.g., 8.2 mmol dm(-3) in mature maternal milk) to high values (0.14 mol dm(-3) in blood plasma). While many data on the concentration of Na(+) and K(+) in various fluids are available, the information on other alkali metal cations is scarce. Since many vital functions depend on the network of interactions occurring in various biofluids, this chapter reviews their complex formation with phosphates, nucleotides, amino acids, and related ligands of biological relevance. Literature data on this topic are quite rare if compared to other cations. Generally, the stability of alkali metal ion complexes of organic and inorganic ligands is rather low (usually log K < 2) and depends on the charge of the ligand, owing to the ionic nature of the interactions. At the same time, the size of the cation is an important factor that influences the stability: very often, but not always (e.g., for sulfate), it follows the trend Li(+) > Na(+) > K(+) > Rb(+) > Cs(+). For example, for citrate it is: log K ML = 0.88, 0.80, 0.48, 0.38, and 0.13 at 25 °C and infinite dilution. Some considerations are made on the main aspects related to the difficulties in the determination of weak complexes. The importance of the alkali metal ion complexes was also studied in the light of modelling natural fluids and in the use of these cations as probes for different processes. Some empirical relationships are proposed for the dependence of the stability constants of Na(+) complexes on the ligand charge, as well as for correlations among log K values of NaL, KL or LiL species (L = generic ligand). PMID:26860301

  15. 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...

  16. Influence of PbCl2 content in PbI2 solution of DMF on the absorption, crystal phase, morphology of lead halide thin films and photovoltaic performance in planar perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Wang, Mao; Shi, Chengwu; Zhang, Jincheng; Wu, Ni; Ying, Chao

    2015-11-01

    In this paper, the influence of PbCl2 content in PbI2 solution of DMF on the absorption, crystal phase and morphology of lead halide thin films was systematically investigated and the photovoltaic performance of the corresponding planar perovskite solar cells was evaluated. The result revealed that the various thickness lead halide thin film with the small sheet-like, porous morphology and low crystallinity can be produced by adding PbCl2 powder into PbI2 solution of DMF as a precursor solution. The planar perovskite solar cell based on the 300-nm-thick CH3NH3PbI3-xClx thin film by the precursor solution with the mixture of 0.80 M PbI2 and 0.20 M PbCl2 exhibited the optimum photoelectric conversion efficiency of 10.12% along with an open-circuit voltage of 0.93 V, a short-circuit photocurrent density of 15.70 mA cm-2 and a fill factor of 0.69.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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

  2. 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)

  3. 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.

  4. Enthalpies of formation of CaAl4O7 and CaAl12O19 (hibonite) by high temperature, alkali borate solution calorimetry

    NASA Technical Reports Server (NTRS)

    Geiger, C. A.; Kleppa, O. J.; Grossman, L.; Mysen, B. O.; Lattimer, J. M.

    1988-01-01

    Enthalpies of formation were determined for two calcium aluminate phases, CaAl4O7 and CaAl12O19, using high-temperature alkali borate solution calorimetry. The aluminates were synthesized by multiple-cycle heating and grinding stoichiometric mixtures of CaCO3 and Al2O3, and the products were characteized by X-ray diffraction and SEM microbeam analysis. The data on impurities (CaAl4O7 was found to be about 89.00 percent pure by weight and the CaAl12O19 samples about 91.48 percent pure) were used to correct the heat of solution values of the synthetic products. The enthalpies of formation, at 1063 K, from oxides, were found to be equal to -(25.6 + or - 4.7) kJ/g.f.w. for CaAl4O7 and -(33.0 + or - 9.7) kJ/g.f.w. for CaAl12O19; the respective standard enthalpies of formation from elements, at 298 K, were estimated to be -4007 + or - 5.2 kJ/g.f.w. and -10,722 + or - 12 kJ/g.f.w.

  5. Comment on ``Measurements of the hydration numbers for halide ions by the mass spectrometric method of field evaporation of ions out of solution'' [Chem. Phys. Lett. 242 (1995) 390

    NASA Astrophysics Data System (ADS)

    Symons, Martyn C. R.

    2000-08-01

    It has been suggested by Dunsyuryun, Karpov and Morozov that two different terms should be used to describe the solvation of halide ions in aqueous solutions. The term co-ordination number gives the primary `solvation number' (ca. 6), whilst the term hydration number gives the number of water molecules that stay co-ordinated to the anions as they move through the liquid (ca. 2). Here it is suggested that since these two terms are widely used to mean the same thing, it is better not to change one of them. It is also suggested that the number of water molecules that move with ions is variable and ill defined and that it is not appropriate to specify a precise number for this.

  6. Mixed-Halide CH3 NH3 PbI3-x Xx (X=Cl, Br, I) Perovskites: Vapor-Assisted Solution Deposition and Application as Solar Cell Absorbers.

    PubMed

    Sedighi, Rahime; Tajabadi, Fariba; Shahbazi, Saeed; Gholipour, Somayeh; Taghavinia, Nima

    2016-08-01

    There have been recent reports on the formation of single-halide perovskites, CH3 NH3 PbX3 (X=Cl, Br, I), by means of vapor-assisted solution processing. Herein, the successful formation of mixed-halide perovskites (CH3 NH3 PbI3-x Xx ) by means of a vapor-assisted solution method at ambient atmosphere is reported. The perovskite films are synthesized by exposing PbI2 film to CH3 NH3 X (X=I, Br, or Cl) vapor. The prepared perovskite films have uniform surfaces with good coverage, as confirmed by SEM images. The inclusion of chlorine and bromine into the structure leads to a lower temperature and shorter reaction time for optimum perovskite film formation. In the case of CH3 NH3 PbI3-x Clx , the optimum reaction temperature is reduced to 100 °C, and the resulting phases are CH3 NH3 PbI3 (with trace Cl) and CH3 NH3 PbCl3 with a ratio of about 2:1. In the case of CH3 NH3 PbI3-x Brx , single-phase CH3 NH3 PbI2 Br is formed in a considerably shorter reaction time than that of CH3 NH3 PbI3 . The mesostructured perovskite solar cells based on CH3 NH3 PbI3 films show the best optimal power conversion efficiency of 13.5 %, whereas for CH3 NH3 PbI3-x Clx and CH3 NH3 PbI3-x Brx the best recorded efficiencies are 11.6 and 10.5 %, respectively. PMID:27124622

  7. Selective Chemical Conversion of Sugars in Aqueous Solutions without Alkali to Lactic Acid Over a Zn-Sn-Beta Lewis Acid-Base Catalyst

    NASA Astrophysics Data System (ADS)

    Dong, Wenjie; Shen, Zheng; Peng, Boyu; Gu, Minyan; Zhou, Xuefei; Xiang, Bo; Zhang, Yalei

    2016-05-01

    Lactic acid is an important platform molecule in the synthesis of a wide range of chemicals. However, in aqueous solutions without alkali, its efficient preparation via the direct catalysis of sugars is hindered by a side dehydration reaction to 5-hydroxymethylfurfural due to Brønsted acid, which originates from organic acids. Herein, we report that a previously unappreciated combination of common two metal mixed catalyst (Zn-Sn-Beta) prepared via solid-state ion exchange synergistically promoted this reaction. In water without a base, a conversion exceeding 99% for sucrose with a lactic acid yield of 54% was achieved within 2 hours at 190 °C under ambient air pressure. Studies of the acid and base properties of the Zn-Sn-Beta zeolite suggest that the introduction of Zn into the Sn-Beta zeolite sequentially enhanced both the Lewis acid and base sites, and the base sites inhibited a series of side reactions related to fructose dehydration to 5-hydroxymethylfurfural and its subsequent decomposition.

  8. Microgel-like aggregates of isotactic and atactic poly(methacrylic acid) chains in aqueous alkali chloride solutions as evidenced by light scattering.

    PubMed

    Sitar, Simona; Aseyev, Vladimir; Kogej, Ksenija

    2014-10-21

    A comparative light-scattering study of isotactic and atactic poly(methacrylic acid), iPMA and aPMA, respectively, in aqueous solutions with added alkali chlorides, XCl (X = Li, Na, Cs), at 25 °C and XCl concentration of 0.1 mol L(-1), demonstrates that both PMA isomers are strongly associated at low degrees of neutralization, αN (= 0 for aPMA and 0.25 for iPMA), in the presence of all XCls. The shape parameter ρ and the scattering functions suggest that aggregates have the characteristics of microgel particles, with a dense core surrounded by a less dense shell. The extent of aggregation depends on the stereoregular structure of the polymer and on the type of the added cation. Li(+) and Na(+) ions support aggregation better than Cs(+) ions. Besides, iPMA chains are more strongly aggregated than aPMA chains and form particles with a denser core. A model of the aggregation process is suggested for iPMA. At high αN, a slow diffusive process (so-called extraordinary or anomalous mode in diffusion of polyelectrolytes), arising from electrostatic interactions between charged chains, is observed for both PMAs. Results suggest that under the same experimental conditions iPMA is effectively more charged than aPMA. The role of ions in the slow-mode phenomenon is less pronounced than in aggregation. PMID:25137480

  9. Selective Chemical Conversion of Sugars in Aqueous Solutions without Alkali to Lactic Acid Over a Zn-Sn-Beta Lewis Acid-Base Catalyst.

    PubMed

    Dong, Wenjie; Shen, Zheng; Peng, Boyu; Gu, Minyan; Zhou, Xuefei; Xiang, Bo; Zhang, Yalei

    2016-01-01

    Lactic acid is an important platform molecule in the synthesis of a wide range of chemicals. However, in aqueous solutions without alkali, its efficient preparation via the direct catalysis of sugars is hindered by a side dehydration reaction to 5-hydroxymethylfurfural due to Brønsted acid, which originates from organic acids. Herein, we report that a previously unappreciated combination of common two metal mixed catalyst (Zn-Sn-Beta) prepared via solid-state ion exchange synergistically promoted this reaction. In water without a base, a conversion exceeding 99% for sucrose with a lactic acid yield of 54% was achieved within 2 hours at 190 °C under ambient air pressure. Studies of the acid and base properties of the Zn-Sn-Beta zeolite suggest that the introduction of Zn into the Sn-Beta zeolite sequentially enhanced both the Lewis acid and base sites, and the base sites inhibited a series of side reactions related to fructose dehydration to 5-hydroxymethylfurfural and its subsequent decomposition. PMID:27222322

  10. Chemical equilibrium model for interfacial activity of crude oil in aqueous alkaline solution: the effects of pH, alkali and salt

    SciTech Connect

    Chan, M.; Yen, T.F.

    1980-11-01

    A chemical equilibrium model for interfacial activity of crude in aqueous alkaline solution is proposed. The model predicts the observed effects of pH and concentrations of alkali and salt on the interfacial tension (IFT). The model proposed was shown to describe the observed effects of acid content, pH, and sodium ions on the interfacial activity of crude oil in water. Once the pH of the interface reaches the pKa of the acids, sometimes with the help of addition of some salt, the IFT experiences a sudden steep drop to the range of 10/sup -2/ dynes/cm. After that, further addition of sodium either in the form of NaOH or NaCl is going to increase the IFT due to a shift of equilibriumn to the formation of undissociated soap. This was confirmed by the difference in the observed effect of sodium on the IFT of the extracted soap molecules which are dissociated easily and those which are associated highly and precipitated easily. These soap molecules have dissociation constant values ranging from below 10/sup -2/ to above one. 13 references.

  11. Selective Chemical Conversion of Sugars in Aqueous Solutions without Alkali to Lactic Acid Over a Zn-Sn-Beta Lewis Acid-Base Catalyst

    PubMed Central

    Dong, Wenjie; Shen, Zheng; Peng, Boyu; Gu, Minyan; Zhou, Xuefei; Xiang, Bo; Zhang, Yalei

    2016-01-01

    Lactic acid is an important platform molecule in the synthesis of a wide range of chemicals. However, in aqueous solutions without alkali, its efficient preparation via the direct catalysis of sugars is hindered by a side dehydration reaction to 5-hydroxymethylfurfural due to Brønsted acid, which originates from organic acids. Herein, we report that a previously unappreciated combination of common two metal mixed catalyst (Zn-Sn-Beta) prepared via solid-state ion exchange synergistically promoted this reaction. In water without a base, a conversion exceeding 99% for sucrose with a lactic acid yield of 54% was achieved within 2 hours at 190 °C under ambient air pressure. Studies of the acid and base properties of the Zn-Sn-Beta zeolite suggest that the introduction of Zn into the Sn-Beta zeolite sequentially enhanced both the Lewis acid and base sites, and the base sites inhibited a series of side reactions related to fructose dehydration to 5-hydroxymethylfurfural and its subsequent decomposition. PMID:27222322

  12. 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.

  13. 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.

  14. 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

  15. 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.

  16. 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.

  17. 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.

  18. 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

  19. 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 ...

  20. 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

  1. 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.

  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. 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.

  4. Electrochemical and in situ STM studies of anomalous phosphate adsorption induced on Zn UPD at Au( 1 1 1 ) in the presence of halide ions in aqueous phosphate solutions

    NASA Astrophysics Data System (ADS)

    Takahashi, Shin; Aramata, Akiko; Nakamura, Mitsuhiro; Hasebe, Kiyoshi; Taniguchi, Masahiro; Taguchi, Satoshi; Yamagishi, Akihiko

    2002-06-01

    Underpotential deposition (UPD) of Zn 2+ at Au(1 1 1) was studied in the phosphate solutions with and without halide ions (Cl -, Br -, and I -) by cyclic voltammetry and in situ STM for the evaluation of the anion adsorption induced on the Zn UPD. The order of the strength of anion adsorption induced on Zn UPD was found to be different from the order of specific adsorption strength of I ->Br ->Cl ->PO 43-⩾SO 42- at an Au substrate electrode. This anomalous tendency of anion adsorption induced on UPD Zn at Au seems to be identical with the cases of sulfate and phosphate adsorption induced on UPD Zn at a Pt electrode in the presence of chloride, being confirmed by radiotracer method. Such anomalous phosphate adsorption induced on Zn UPD was found to take place at Au(1 1 1) not only in the presence of chloride or bromide, but also even in the presence of iodide in the phosphate solution. The in situ STM images of Zn UPD were observed at Au(1 1 1) in the phosphate solution with iodide ions. At -200 mV (saturated calomel electrode; SCE) where the iodide adsorbs at substrate Au(1 1 1), the STM image was c(p× 3R30°) , and in the Zn UPD region, the STM image became ( 3× 3)R30° . The latter image is discussed to be assigned to the image in the absence of iodide, i.e., that the adsorbed anions induced at Zn UPD are phosphate species even in the solution containing iodide ions.

  5. 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

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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

  11. Alkali-treated penicillin G solution is a better option than penicillin G as an alternative source of minor determinants for penicillin skin test.

    PubMed

    Wangrattanasopon, Pongsak; Ruxrungtham, Kiat; Chantaphakul, Hiroshi; Buranapraditkun, Supranee; Klaewsongkram, Jettanong

    2012-01-01

    Both benzylpenicilloyl-polylysine (PPL) and minor determinant mixture (MDM) are the recommended standard reagents for penicillin skin testing. However, penicillin G is commonly suggested as an alternative source of minor determinants. This study evaluated the accuracy of penicillin G and alkali-treated penicillin G compared with the standardized MDM for skin testing. Sixty-eight patients with histories of allergies to penicillin or semisynthetic penicillins were skin tested with commercial Kit penicillin allergenic determinants (DAP) (PPL and DAP-MDM; Diater Laboratorios, Madrid, Spain). The in-house MDM (IH-MDM), prepared by alkali-treated aged penicillin, and fresh penicillin G sodium (PGs) were tested alongside DAP-MDM. Positive penicillin skin test results were identified in 22 patients (32.4%) using commercial reagents (PPL+ DAP-MDM) and 19 of them reacted to DAP-MDM alone or together with PPL. The accuracy of IH-MDM and PGs compared with DAP-MDM was 89.7 and 76.5%, respectively. Our study shows that alkali-treated penicillin G is a better option than penicillin G as an alternative source of MDM for skin testing in case the commercialized MDM is not available. Minor determinants play a significant role for penicillin allergy in Thailand and should be included in the penicillin skin test panel to verify suspected cases of penicillin allergy. (ClinicalTrials.gov number: NCT00789217). PMID:22525392

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. Hydrogen bonding Part 54. NMR study of the effects of anesthetics on hydration of choline, acetylcholine and tetraethylammonium halides in aqueous solution

    NASA Astrophysics Data System (ADS)

    Akin, Anne C.; Harmon, Kenneth M.

    1994-03-01

    The onset and development of 14N to CH coupling on sequential dilution of saturated solutions of the chloride and bromide salts of choline, acetylcholine and tetraethylammonium cations were used to determine the effect of the anesthetic substances chloroform, methane, argon and diethyl ether on the formation of primary and secondary hydration structures. The addition of anesthetics tends to reduce the number of H 2O molecules required to form the primary structure. Anesthetics reduce the number of H 2O molecules in the secondary structures of salts that form secondary structures in the absence of anesthetics, and promote the formation of secondary structures for salts that do not form secondary structures in the absence of anesthetics. These phenomena are discussed in terms of competition between salt and anesthetic substance as structure formers. Anesthetics appear to disrupt the "iceberg" water of hydration of acetylcholine; this effect might play some role in their action in anesthesia.

  19. 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.

  20. 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.

  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. 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.

  3. 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.

  4. 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.

  5. Alkali metal ionization detector

    DOEpatents

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

    1978-01-01

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

  6. 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. 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.

  8. 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

  9. 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.

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

    DOEpatents

    Sharp, David W.

    1980-01-01

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

  11. 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.

  12. 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.

  13. 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

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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...

  19. 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.

  20. 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)

  1. 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+.

  2. 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.

  3. 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.

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

    PubMed

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

    2012-06-14

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

  5. 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

  6. 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

  7. 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.

  8. 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

  9. 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

  10. 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

  11. 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

  12. Model to explain the effects of halide ions on the increase in surface enhanced Raman spectral intensity over time

    NASA Astrophysics Data System (ADS)

    Cole, Michael A.

    Understanding the mechanisms responsible for the large increase in spectral intensity when molecules are adsorbed to nanoparticle surfaces such as occurs during surface enhanced Raman (SER) spectroscopy will allow scientists to probe ever smaller scales, even allowing single molecule detection. One particular scenario that increased the SER scattering efficiency was the addition of halide ions to Rhodamine 6G (R6G)-ethanol solution. This thesis presents a theoretical model explaining the effects of halide ions on the SER spectral intensity of the Rhodamine 6G (R6G) molecule when co-adsorbed to a silver nanoparticle surface. Glaspell et al. 2005, found a linear correlation between the increase in spectral intensities of selected vibrational normal modes of R6G over time and the polarizabilities of co-adsorbed halide ions. When the R6G molecule co-adsorbs to the silver nanoparticle surface with the halide ions, the molecule is exposed to three external electric fields that add vectorially, creating a total external electric field. Modelling the fields from the halide ions and the silver nanoparticles as electric dipole fields introduces the polarizability of the halide ion linearly into the Raman spectral intensity equation. This model also shows that there is a necessary interaction between the halide ions and the silver nanoparticle surface in order to see the effects as described by Glaspell et al. Furthermore, we will present experimental results that show that there is a necessary interaction between the halide ions and the nanoparticle surface. Without this interaction there was no increase in the SER spectral intensity of R6G or pyridine molecules in solution with the halide ions but without the silver nanoparticles.

  13. Tuning the Optical Properties of Cesium Lead Halide Perovskite Nanocrystals by Anion Exchange Reactions

    PubMed Central

    2015-01-01

    We demonstrate that, via controlled anion exchange reactions using a range of different halide precursors, we can finely tune the chemical composition and the optical properties of presynthesized colloidal cesium lead halide perovskite nanocrystals (NCs), from green emitting CsPbBr3 to bright emitters in any other region of the visible spectrum, and back, by displacement of Cl– or I– ions and reinsertion of Br– ions. This approach gives access to perovskite semiconductor NCs with both structural and optical qualities comparable to those of directly synthesized NCs. We also show that anion exchange is a dynamic process that takes place in solution between NCs. Therefore, by mixing solutions containing perovskite NCs emitting in different spectral ranges (due to different halide compositions) their mutual fast exchange dynamics leads to homogenization in their composition, resulting in NCs emitting in a narrow spectral region that is intermediate between those of the parent nanoparticles. PMID:26214734

  14. Tuning the Optical Properties of Cesium Lead Halide Perovskite Nanocrystals by Anion Exchange Reactions.

    PubMed

    Akkerman, Quinten A; D'Innocenzo, Valerio; Accornero, Sara; Scarpellini, Alice; Petrozza, Annamaria; Prato, Mirko; Manna, Liberato

    2015-08-19

    We demonstrate that, via controlled anion exchange reactions using a range of different halide precursors, we can finely tune the chemical composition and the optical properties of presynthesized colloidal cesium lead halide perovskite nanocrystals (NCs), from green emitting CsPbBr3 to bright emitters in any other region of the visible spectrum, and back, by displacement of Cl(-) or I(-) ions and reinsertion of Br(-) ions. This approach gives access to perovskite semiconductor NCs with both structural and optical qualities comparable to those of directly synthesized NCs. We also show that anion exchange is a dynamic process that takes place in solution between NCs. Therefore, by mixing solutions containing perovskite NCs emitting in different spectral ranges (due to different halide compositions) their mutual fast exchange dynamics leads to homogenization in their composition, resulting in NCs emitting in a narrow spectral region that is intermediate between those of the parent nanoparticles. PMID:26214734

  15. 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

  16. 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.

  17. 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

  18. Effect of cavitation on removal of alkali elements from coal

    NASA Astrophysics Data System (ADS)

    Srivalli, H.; Nirmal, L.; Nagarajan, R.

    2015-12-01

    The main impurities in coal are sulphur, ash and alkali. On combustion, the volatile forms of these impurities are either condensed on the boilers, or emitted in the form of potentially hazardous gases. The alkali elements present in coal help the fly ash particles adhere to boiler surfaces by providing a wet surface on which collection of these particles can take place. Use of ultrasonic techniques in cleaning of coal has stirred interest among researchers in recent times. Extraction of alkali elements by cavitation effect using low-frequency ultrasound, in the presence of reagents (HNO3 and H2O2) is reported in this paper. Powdered coal was dissolved with the reagent and exposed to ultrasonic fields of various frequencies at different time intervals. The treated solution is filtered and tested for alkali levels.

  19. Halide anion dependence of ionic surfactant adsorption in air/water interface

    NASA Astrophysics Data System (ADS)

    Kim, Doseok; Wang, Wenjie; Sung, Woongmo; Ao, Mingqi; Vaknin, David

    2014-03-01

    It was recently proposed that there is surface excess of halide anions at the air/water interface, and more surface excess of I- than Br- or Cl-, which cannot be explained by Debye-Huckel theory. In case of charged surfaces such as Gibbs monolayer consisting of cationic surfactant molecules, surface excess of anions can also be expected. In this study, by using surface-sensitive grazing angle X-ray fluorescence in conjunction with surface tension measurement, we investigated adsorption behavior of [C12mim]Cl, [C12mim]Br, [C12mim]I aqueous solutions, in which the surface is first covered by [C12mim]+ cations at low concentrations, and the adsorption of the halide anions to this charged interface would follow with the increase in the concentration of solutes. From the surface tension measurements, it was observed that critical micelle concentration of [C12mim]I solution was 4.6 mM, much smaller than that of [C12mim]Cl (16.7 mM) indicating surface activity of surfactant increases with size of halide anions. From X-ray fluorescence, surface excess of halide anion was measured quantitatively from the interface of these solutions. By putting NaCl and NaI in [C12mim]I and [C12mim]Cl solutions, respectively, competition between Cl- and I- adsorption was investigated, to find that I- has stronger adsorption on the charged surface than Cl-.

  20. 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)

  1. 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.

  2. 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.

  3. 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.

  4. Lead- and alkali-metal-free BaTiO3-Bi(Mg0.5Ti0.5)O3-BiFeO3 solid-solution thin films with high dielectric constant prepared on Si substrates by solution-based method

    NASA Astrophysics Data System (ADS)

    Kimura, Junichi; Mohamed-Tahar, Chentir; Shimizu, Takao; Uchida, Hiroshi; Funakubo, Hiroshi

    2014-09-01

    Lead- and alkali-metal-free BaTiO3-Bi(Mg0.5Ti0.5)O3-BiFeO3 solid-solution thin films were prepared on (111)cSrRuO3/(111)Pt/TiO2/SiO2/(100)Si substrates by chemical solution deposition (CSD) and their crystal structure and dielectric properties were investigated. The lattice spacing as a function of z/(x + z) in xBaTiO3-0.1Bi(Mg0.5Ti0.5)O3-zBiFeO3 indicated the existence of phase boundaries (pseudocubic/rhombohedral) in the range of z/(x + z) = 0.33-0.56, where the relatively high relative dielectric constant, ɛr, of above 800 was obtained. On the other hand, dielectric loss, tan δ, of below 0.2 was confirmed in the range z/(x + z) = 0-0.87, which rapidly increased toward z/(x + z) = 1.0. The relatively high ɛr values of these films deposited on Si substrates by a solution-based process suggest that they can be used as alternative to Pb(Zr,Ti)O3, KNbO3, and (Bi1/2Na1/2)TiO3-based films.

  5. High-Efficiency Flexible Solar Cells Based on Organometal Halide Perovskites.

    PubMed

    Wang, Yuming; Bai, Sai; Cheng, Lu; Wang, Nana; Wang, Jianpu; Gao, Feng; Huang, Wei

    2016-06-01

    Flexible and light-weight solar cells are important because they not only supply power to wearable and portable devices, but also reduce the transportation and installation cost of solar panels. High-efficiency organometal halide perovskite solar cells can be fabricated by a low-temperature solution process, and hence are promising for flexible-solar-cell applications. Here, the development of perovskite solar cells is briefly discussed, followed by the merits of organometal halide perovskites as promising candidates as high-efficiency, flexible, and light-weight photovoltaic materials. Afterward, recent developments of flexible solar cells based on perovskites are reviewed. PMID:26669326

  6. Plasmonic characterization of photo-induced silver nanoparticles extracted from silver halide based TEM film

    NASA Astrophysics Data System (ADS)

    Sudheer, Tiwari, P.; Varshney, G. K.; Rai, V. N.; Srivastava, A. K.

    2016-05-01

    The plasmonic responses of silver nanoparticles extracted from silver halide based electron microscope film are investigated. Photo-reduction process is carried out to convert the silver halide grains into the metallic silver. The centrifuge technique is used for separating the silver nanoparticles from the residual solution. Morphological study performed by field emission scanning electron microscope (FESEM) shows that all the nanoparticles have an average diameter of ~120 nm with a high degree of mono dispersion in size. The localized surface plasmon resonance (LSPR) absorption peak at ~537 nm confirms the presence of large size silver nanoparticles.

  7. Influence of halide flux on the crystallinity, microstructure and thermoluminescence properties of CdSiO{sub 3}:Co{sup 2+} nanophosphor

    SciTech Connect

    Manjunatha, C.; Nagabhushana, B.M.; Sunitha, D.V.; Nagabhushana, H.; Sharma, S.C.; Chakradhar, R.P.S.

    2013-01-15

    Graphical abstract: TL glow curves of CdSiO{sub 3}:Co{sup 2+} different alkali flux (inset without adding flux). Display Omitted Highlights: ► CdSiO{sub 3}:Co{sup 2+} (1–7 mol%) nanocrystalline phosphors synthesized by combustion route. ► Flux effect on thermoluminescence behavior of CdSiO{sub 3}:Co{sup 2+} reported for first time. ► Addition of 2 wt% of flux would drastically enhance the TL properties. ► Well resolved single glow peak at ∼170 °C was recorded for all the samples. ► Among all the alkali flux, NaCl shows highest TL peak intensity. -- Abstract: CdSiO{sub 3}:Co{sup 2+} (1–7 mol %) nanophosphors have been prepared via solution combustion method with post calcination at 800 °C for 2 h for the first time. The formation of expected monoclinic phase was investigated by Powder X-ray diffraction (PXRD) measurements. The effect of different fluxes like NaF, NaCl, NH{sub 4}F and NH{sub 4}Cl on the crystallinity, phase and morphology of CdSiO{sub 3} was investigated in detail. The crystallinity of the samples can be greatly enhanced by using fluxes rather than increasing the calcination temperature. Scanning electronic micrograph (SEM) image shows that the powder morphologies are highly influenced by flux addition. The addition of 2 wt% of fluxes would drastically enhance the crystallinity when NaCl, NH{sub 4}F and NH{sub 4}Cl fluxes are used. A well resolved single thermoluminescent glow peak at ∼170 °C was recorded for all the samples. Among all the halide fluxes, NaCl flux was found to be the potential one in enhancing the TL peak intensity along with crystallinity.

  8. Alkali-aggregate reactivity of typical siliceious glass and carbonate rocks in alkali-activated fly ash based geopolymers

    NASA Astrophysics Data System (ADS)

    Lu, Duyou; Liu, Yongdao; Zheng, Yanzeng; Xu, Zhongzi; Shen, Xiaodong

    2013-08-01

    For exploring the behaviour of alkali-aggregate reactivity (AAR) in alkali-activated geopolymeric materials and assessing the procedures for testing AAR in geopolymers, the expansion behaviour of fly ash based geopolymer mortars with pure silica glass and typical carbonate rocks were studied respectively by curing at various conditions, i.e. 23°C and 38°C with relative humidity over 95%, immersed in 1M NaOH solution at 80°C. Results show that, at various curing conditions, neither harmful ASR nor harmful ACR was observed in geopolymers with the criteria specified for OPC system. However, with the change of curing conditions, the geopolymer binder and reactive aggregates may experience different reaction processes leading to quite different dimensional changes, especially with additional alkalis and elevated temperatures. It suggests that high temperature with additional alkali for accelerating AAR in traditional OPC system may not appropriate for assessing the alkali-aggregate reactivity behaviour in geopolymers designed for normal conditions. On the other hand, it is hopeful to control the dimensional change of geopolymer mortar or concrete by selecting the type of aggregates and the appropriate curing conditions, thus changing the harmful AAR in OPC into beneficial AAR in geopolymers and other alkali-activated cementitious systems.

  9. 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.

  10. 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.

  11. 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)

  12. 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.

  13. Tunable Near-Infrared Luminescence in Tin Halide Perovskite Devices.

    PubMed

    Lai, May L; Tay, Timothy Y S; Sadhanala, Aditya; Dutton, Siân E; Li, Guangru; Friend, Richard H; Tan, Zhi-Kuang

    2016-07-21

    Infrared emitters are reasonably rare in solution-processed materials. Recently, research into hybrid organo-lead halide perovskite, originally popular in photovoltaics,1-3 has gained traction in light-emitting diodes (LED) due to their low-cost solution processing and good performance.4-9 The lead-based electroluminescent materials show strong colorful emission in the visible region, but lack emissive variants further in the infrared. The concerns with the toxicity of lead may, additionally, limit their wide-scale applications. Here, we demonstrate tunable near-infrared electroluminescence from a lead-free organo-tin halide perovskite, using an ITO/PEDOT:PSS/CH3NH3Sn(Br1-xIx)3/F8/Ca/Ag device architecture. In our tin iodide (CH3NH3SnI3) LEDs, we achieved a 945 nm near-infrared emission with a radiance of 3.4 W sr(-1) m(-2) and a maximum external quantum efficiency of 0.72%, comparable with earlier lead-based devices. Increasing the bromide content in these tin perovskite devices widens the semiconductor bandgap and leads to shorter wavelength emissions, tunable down to 667 nm. These near-infrared LEDs could find useful applications in a range of optical communication, sensing and medical device applications. PMID:27336412

  14. 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)...

  15. 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.

  16. 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

  17. ELECTROLYTIC REDUCTION OF NITRIC ACID SOLUTIONS

    DOEpatents

    Alter, H.W.; Barney, D.L.

    1958-09-30

    A process is presented for the treatment of radioactivc waste nitric acid solutions. The nitric acid solution is neutralized with an alkali metal hydroxide in an amount sufficient to precipitate insoluble hydroxides, and after separation of the precipitate the solution is electrolyzed to convert the alkali nitrate formed, to alkali hydroxide, gaseous ammonla and oxygen. The solution is then reusable after reducing the volume by evaporating the water and dissolved ammonia.

  18. Enhancement of Exciton Emission in Lead Halide-Based Layered Perovskites by Cation Mixing.

    PubMed

    Era, Masanao; Komatsu, Yumeko; Sakamoto, Naotaka

    2016-04-01

    Spin-coated films of a lead halide, PbX: X = I and Br, layered perovskites having cyclohexenylethyl ammonium molecule as an organic layer, which were mixed with other metal halide-based layered perovskites consisting of various divalent metal halides (for example, Ca2, Cdl2, FeI2, SnBr2 and so on), were prepared. The results of X-ray diffraction measurements exhibited that solid solution formation between PbX-based layered perovskite and other divalent metal halide-based layered perovskites was observed up to very high molar concentration of 50 molar% in the mixed film samples when divalent cations having ionic radius close to that of Pb2+ were employed. In the solid solution films, the exciton emission was much enhanced at room temperature. Exciton emission intensity of Pbl-based layered perovskite mixed with Cal-based layered perovskite (20 molar%) is about 5 times large that of the pristine Pbl-based layered perovskite, and that of PbBr-based layered perovskite mixed with SnBr-based layered perovskite (20 molar%) was also about 5 times large that of the pristine PbBr-based layered perovskite at room temperature. PMID:27451628

  19. 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.

  20. 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

  1. Physiological Evaluation of Alkali-Salt Tolerance of Thirty Switchgrass (Panicum virgatum) Lines.

    PubMed

    Hu, Guofu; Liu, Yiming; Zhang, Xunzhong; Yao, Fengjiao; Huang, Yan; Ervin, Erik H; Zhao, Bingyu

    2015-01-01

    Soil salt-alkalization is a major limiting factor for crop production in many regions. Switchgrass (Panicum virgatum L.) is a warm-season C4 perennial rhizomatous bunchgrass and a target lignocellulosic biofuel species. The objective of this study was to evaluate relative alkali-salt tolerance among 30 switchgrass lines. Tillers of each switchgrass line were transplanted into pots filled with fine sand. Two months after transplanting, plants at E5 developmental stage were grown in either half strength Hoagland's nutrient solution with 0 mM Na+ (control) or half strength Hoagland's nutrient solution with 150 mM Na+ and pH of 9.5 (alkali-salt stress treatment) for 20 d. Alkali-salt stress damaged cell membranes [higher electrolyte leakage (EL)], reduced leaf relative water content (RWC), net photosynthetic rate (Pn), stomatal conductance (gs), and transpiration rate (Tr). An alkali-salt stress tolerance trait index (ASTTI) for each parameter was calculated based on the ratio of the value under alkali-salt stress and the value under non-stress conditions for each parameter of each line. Relative alkali-salt tolerance was determined based on principal components analysis and cluster analysis of the physiological parameters and their ASTTI values. Significant differences in alkali-salt stress tolerance were found among the 30 lines. Lowland lines TEM-SEC, Alamo, TEM-SLC and Kanlow were classified as alkali-salt tolerant. In contrast, three lowland lines (AM-314/MS-155, BN-13645-64) and two upland lines (Caddo and Blackwell-1) were classified as alkali-salt sensitive. The results suggest wide variations exist in alkali-salt stress tolerance among the 30 switchgrass lines. The approach of using a combination of principal components and cluster analysis of the physiological parameters and related ASTTI is feasible for evaluating alkali-salt tolerance in switchgrass. PMID:26146987

  2. Release and sorption of alkali metals in coal conversion

    SciTech Connect

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

    1998-07-01

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

  3. 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

  4. Detection of alkali-silica reaction swelling in concrete by staining

    DOEpatents

    Guthrie, Jr., George D.; Carey, J. William

    1998-01-01

    A method using concentrated aqueous solutions of sodium cobaltinitrite and rhodamine B is described which can be used to identify concrete that contains gels formed by the alkali-silica reaction (ASR). These solutions present little health or environmental risk, are readily applied, and rapidly discriminate between two chemically distinct gels; K-rich, Na--K--Ca--Si gels are identified by yellow staining, and alkali-poor, Ca--Si gels are identified by pink staining.

  5. Detection of alkali-silica reaction swelling in concrete by staining

    DOEpatents

    Guthrie, G.D. Jr.; Carey, J.W.

    1998-04-14

    A method using concentrated aqueous solutions of sodium cobalt nitrite and rhodamine B is described which can be used to identify concrete that contains gels formed by the alkali-silica reaction (ASR). These solutions present little health or environmental risk, are readily applied, and rapidly discriminate between two chemically distinct gels; K-rich, Na-K-Ca-Si gels are identified by yellow staining, and alkali-poor, Ca-Si gels are identified by pink staining.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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

  12. 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

  13. 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.

  14. 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.

  15. Persistent dopants and phase segregation in organolead mixed-halide perovskites

    DOE PAGESBeta

    Rosales, Bryan A.; Men, Long; Cady, Sarah D.; Hanrahan, Michael P.; Rossini, Aaron J.; Vela, Javier

    2016-07-25

    Organolead mixed-halide perovskites such as CH3NH3PbX3–aX'a (X, X' = I, Br, Cl) are interesting semiconductors because of their low cost, high photovoltaic power conversion efficiencies, enhanced moisture stability, and band gap tunability. Using a combination of optical absorption spectroscopy, powder X-ray diffraction (XRD), and, for the first time, 207Pb solid state nuclear magnetic resonance (ssNMR), we probe the extent of alloying and phase segregation in these materials. Because 207Pb ssNMR chemical shifts are highly sensitive to local coordination and electronic structure, and vary linearly with halogen electronegativity and band gap, this technique can provide the true chemical speciation and compositionmore » of organolead mixed-halide perovskites. We specifically investigate samples made by three different preparative methods: solution phase synthesis, thermal annealing, and solid phase synthesis. 207Pb ssNMR reveals that nonstoichiometric dopants and semicrystalline phases are prevalent in samples made by solution phase synthesis. We show that these nanodomains are persistent after thermal annealing up to 200 °C. Further, a novel solid phase synthesis that starts from the parent, single-halide perovskites can suppress phase segregation but not the formation of dopants. Our observations are consistent with the presence of miscibility gaps and spontaneous spinodal decomposition of the mixed-halide perovskites at room temperature. This underscores how strongly different synthetic procedures impact the nanostructuring and composition of organolead halide perovskites. In conclusion, better optoelectronic properties and improved device stability and performance may be achieved through careful manipulation of the different phases and nanodomains present in these materials.« less

  16. Recovery of Ga(III) by Raw and Alkali Treated Citrus limetta Peels

    PubMed Central

    2014-01-01

    Alkali treated Citrus limetta peels were used for recovery of Ga(III) from its aqueous solution. The raw and alkali treated peels were characterized for functional groups. The efficiency of adsorption increased from 47.62 mg/g for raw peels to 83.33 mg/g for alkali treated peels. Between pH 1 and 3, the adsorption increased and thereafter decreased drastically. The adsorption followed pseudosecond order kinetics and Langmuir isotherm gave the best fit for the experimental data. Desorption studies showed 95.28% desorption after 3 cycles for raw peels while it was 89.51% for alkali treated peels. Simulated Bayer liquor showed 39.57% adsorption for gallium ions on raw peels which was enhanced to 41.13% for alkali treated peels.

  17. 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

  18. 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

  19. 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.

  20. Seed-mediated growth of palladium nanocrystals: the effect of pseudo-halide thiocyanate ions.

    PubMed

    Zhang, Ling; Niu, Wenxin; Xu, Guobao

    2011-02-01

    In synthesis in a solution phase, adsorbates such as halides can interact selectively with different metal crystal facets and affect the final morphology of nanocrystals. Pseudo-halide thiocyanate ions (SCN-) can also adsorb on the metal surface, but they have never been used for the synthesis of shape-controlled colloidal metal nanocrystals. In this study, we first investigated the effect of SCN- on the morphology of palladium nanocrystals through a seed-mediated growth method. The presence of 1 µM SCN- in the growth solutions could lead to the formation of palladium polyhedra: truncated rhombic dodecahedra enclosed by twelve {110}, eight {111} and six {100} facets. The products were nanocubes enclosed with six {100} facets if cetyltrimethylammonium bromide (CTAB) was the only capping agent. Meanwhile, the mechanism of the effect of SCN- on the morphology of Pd nanocrystals is discussed. PMID:21170425

  1. Giant photostriction in organic-inorganic lead halide perovskites.

    PubMed

    Zhou, Yang; You, Lu; Wang, Shiwei; Ku, Zhiliang; Fan, Hongjin; Schmidt, Daniel; Rusydi, Andrivo; Chang, Lei; Wang, Le; Ren, Peng; Chen, Liufang; Yuan, Guoliang; Chen, Lang; Wang, Junling

    2016-01-01

    Among the many materials investigated for next-generation photovoltaic cells, organic-inorganic lead halide perovskites have demonstrated great potential thanks to their high power conversion efficiency and solution processability. Within a short period of about 5 years, the efficiency of solar cells based on these materials has increased dramatically from 3.8 to over 20%. Despite the tremendous progress in device performance, much less is known about the underlying photophysics involving charge-orbital-lattice interactions and the role of the organic molecules in this hybrid material remains poorly understood. Here, we report a giant photostrictive response, that is, light-induced lattice change, of >1,200 p.p.m. in methylammonium lead iodide, which could be the key to understand its superior optical properties. The strong photon-lattice coupling also opens up the possibility of employing these materials in wireless opto-mechanical devices. PMID:27044485

  2. Recent progress and challenges of organometal halide perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Yang, Liyan; Barrows, Alexander T.; Lidzey, David G.; Wang, Tao

    2016-02-01

    We review recent progress in the development of organometal halide perovskite solar cells. We discuss different compounds used to construct perovskite photoactive layers, as well as the optoelectronic properties of this system. The factors that affect the morphology of the perovskite active layer are explored, e.g. material composition, film deposition methods, casting solvent and various post-treatments. Different strategies are reviewed that have recently emerged to prepare high performing perovskite films, creating polycrystalline films having either large or small grain size. Devices that are constructed using meso-superstructured and planar architectures are summarized and the impact of the fabrication process on operational efficiency is discussed. Finally, important research challenges (hysteresis, thermal and moisture instability, mechanical flexibility, as well as the development of lead-free materials) in the development of perovskite solar cells are outlined and their potential solutions are discussed.

  3. Giant photostriction in organic–inorganic lead halide perovskites

    PubMed Central

    Zhou, Yang; You, Lu; Wang, Shiwei; Ku, Zhiliang; Fan, Hongjin; Schmidt, Daniel; Rusydi, Andrivo; Chang, Lei; Wang, Le; Ren, Peng; Chen, Liufang; Yuan, Guoliang; Chen, Lang; Wang, Junling

    2016-01-01

    Among the many materials investigated for next-generation photovoltaic cells, organic–inorganic lead halide perovskites have demonstrated great potential thanks to their high power conversion efficiency and solution processability. Within a short period of about 5 years, the efficiency of solar cells based on these materials has increased dramatically from 3.8 to over 20%. Despite the tremendous progress in device performance, much less is known about the underlying photophysics involving charge–orbital–lattice interactions and the role of the organic molecules in this hybrid material remains poorly understood. Here, we report a giant photostrictive response, that is, light-induced lattice change, of >1,200 p.p.m. in methylammonium lead iodide, which could be the key to understand its superior optical properties. The strong photon-lattice coupling also opens up the possibility of employing these materials in wireless opto-mechanical devices. PMID:27044485

  4. Giant photostriction in organic-inorganic lead halide perovskites

    NASA Astrophysics Data System (ADS)

    Zhou, Yang; You, Lu; Wang, Shiwei; Ku, Zhiliang; Fan, Hongjin; Schmidt, Daniel; Rusydi, Andrivo; Chang, Lei; Wang, Le; Ren, Peng; Chen, Liufang; Yuan, Guoliang; Chen, Lang; Wang, Junling

    2016-04-01

    Among the many materials investigated for next-generation photovoltaic cells, organic-inorganic lead halide perovskites have demonstrated great potential thanks to their high power conversion efficiency and solution processability. Within a short period of about 5 years, the efficiency of solar cells based on these materials has increased dramatically from 3.8 to over 20%. Despite the tremendous progress in device performance, much less is known about the underlying photophysics involving charge-orbital-lattice interactions and the role of the organic molecules in this hybrid material remains poorly understood. Here, we report a giant photostrictive response, that is, light-induced lattice change, of >1,200 p.p.m. in methylammonium lead iodide, which could be the key to understand its superior optical properties. The strong photon-lattice coupling also opens up the possibility of employing these materials in wireless opto-mechanical devices.

  5. Interactions between halide anions and a molecular hydrophobic interface.

    PubMed

    Rankin, Blake M; Hands, Michael D; Wilcox, David S; Fega, K Rebecca; Slipchenko, Lyudmila V; Ben-Amotz, Dor

    2013-01-01

    Interactions between halide ions (fluoride and iodide) and t-butyl alcohol (TBA) dissolved in water are probed using a recently developed hydration-shell spectroscopic technique and theoretical cluster and liquid calculations. High ignal-to-noise Raman spectroscopic measurements are combined with multivariate curve resolution (Raman-MCR) to reveal that while there is little interaction between aqueous fluoride ions and TBA, iodide ions break down the tetrahedral hydration-shell structure of TBA and produce a red-shift in its CH stretch frequency, in good agreement with the theoretical effective fragment potential (EFP) molecular dynamics simulations and hybrid quantum/EFP frequency calculations. The results imply that there is a significantly larger probability of finding iodide than fluoride in the first hydration shell of TBA, although the local iodide concentration is apparently not as high as in the surrounding bulk aqueous NaI solution. PMID:23795504

  6. 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.

  7. Photochemical Reaction Dynamics of Halooxides and Nitrosyl Halides

    NASA Astrophysics Data System (ADS)

    Reid, Philip

    2004-03-01

    Recent progress in understanding the environment-dependent reactivity of halooxides and nitrosyl halides is presented. Time-resolved resonance Raman and transient infrared absorption studies of chlorine dioxide (OClO) photochemistry in solution are presented. These studies demonstrate that geminate recombination of the primary ClO and O photofragments results in the reformation of ground-state OClO on the sub-picosecond timescale. These studies also demonstrate that a fraction of photoexcited OClO undergoes photoisomerization to produce ClOO on the tens-of-picoseconds timescale, with ground-state thermal decomposition of this species providing for Cl production on the sub-nanosecond timescale. The discrepancy in formation times for ground-state OClO and ClOO demonstrates that the photoisomer is not produced by geminate recombination, and possible mechanisms for the formation of this intermediate are presented. The excited-state reaction dynamics of nitrosyl chloride (ClNO) that occur following photoexcitation resonant with the "A band" are determined using absolute resonance Raman intensity analysis (RRIA). These studies demonstrate that photoexcitation of solution-phase ClNO promotes evolution along the N-Cl stretch coordinate consistent with N-Cl bond dissociation. Comparative RRIA studies of ClNO dissolved in cyclohexane and acetonitrile reveal that the excited-state structural evolution is solvent dependent; however, the origin of this dependence is related to modification of the ground-state equilibrium geometry with solvent. Finally, femtosecond transient absorption studies reveal that in condensed environments, photoexcitation of ClNO also results in photoisomerization to produce the intermediate species ClON on the picosecond timescale. This observation suggests that photoisomerization is a general feature of halooxide and nitrosyl halide chemistry in condensed environments.

  8. Seed-mediated growth of palladium nanocrystals: The effect of pseudo-halide thiocyanate ions

    NASA Astrophysics Data System (ADS)

    Zhang, Ling; Niu, Wenxin; Xu, Guobao

    2011-02-01

    In synthesis in a solution phase, adsorbates such as halides can interact selectively with different metal crystal facets and affect the final morphology of nanocrystals. Pseudo-halide thiocyanate ions (SCN-) can also adsorb on the metal surface, but they have never been used for the synthesis of shape-controlled colloidal metal nanocrystals. In this study, we first investigated the effect of SCN- on the morphology of palladium nanocrystals through a seed-mediated growth method. The presence of 1 µM SCN- in the growth solutions could lead to the formation of palladium polyhedra: truncated rhombic dodecahedra enclosed by twelve {110}, eight {111} and six {100} facets. The products were nanocubes enclosed with six {100} facets if cetyltrimethylammonium bromide (CTAB) was the only capping agent. Meanwhile, the mechanism of the effect of SCN- on the morphology of Pd nanocrystals is discussed.In synthesis in a solution phase, adsorbates such as halides can interact selectively with different metal crystal facets and affect the final morphology of nanocrystals. Pseudo-halide thiocyanate ions (SCN-) can also adsorb on the metal surface, but they have never been used for the synthesis of shape-controlled colloidal metal nanocrystals. In this study, we first investigated the effect of SCN- on the morphology of palladium nanocrystals through a seed-mediated growth method. The presence of 1 µM SCN- in the growth solutions could lead to the formation of palladium polyhedra: truncated rhombic dodecahedra enclosed by twelve {110}, eight {111} and six {100} facets. The products were nanocubes enclosed with six {100} facets if cetyltrimethylammonium bromide (CTAB) was the only capping agent. Meanwhile, the mechanism of the effect of SCN- on the morphology of Pd nanocrystals is discussed. Electronic supplementary information (ESI) available: Additional SEM, TEM and XRD data. See DOI: 10.1039/c0nr00622j

  9. Electrochemistry of acetylides, nitrides and carbon cathodes in molten halides. Progress report

    SciTech Connect

    Selman, J. R.

    1980-04-01

    Additional experimental data on acetylide solutions in contact with graphite and carbon indicate that intercalation occurs not only in Li/sup +/-containing melts but also in Ca/sup 2 +/ melts. Emf measurements are being carried out to determine the calcium activity in Ca-Al alloys. Proposed work include carbonate reduction to acetylides and the mechanism of the corrosion resistance of Mo in molten halides. (DLC)

  10. 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

  11. Grand Canonical Monte Carlo coupled multiscale simulation for electrochemical and solvent parameters of silver halide systems in water.

    PubMed

    Sudha, V; Harinipriya, S; Sangaranarayanan, M V

    2016-07-01

    Grand Canonical Monte Carlo methods in conjunction with continuum Multiscale simulation to estimate the hydration energies and surface potentials of silver halides as demonstrated elsewhere is employed by incorporating random distribution of molecules, nearest neighbor distances and hydration numbers. The extent of dehydration during each step and the corresponding variation in the hydration numbers are evaluated, assuming the validity of hard spheres. These estimates are then employed to deduce the redox potential of the reaction viz. 2AgX(solution)⇔2Ag(solid)+X2(gas). The dependence of these values on the nature of the halides and solvation characteristics is indicated. PMID:27442589

  12. 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.

  13. 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

  14. 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...

  15. Comparative alkali washing of simulated radioactive sludge

    SciTech Connect

    Fugate, G.A.; Ensor, D.D.; Egan, B.Z.

    1996-10-01

    The treatment of large volumes of radioactive sludge generated from uranium and plutonium recovery processes is a pressing problem in the environmental restoration currently planned at various U.S. Department of Energy sites. This sludge, commonly stored in underground tanks, is mainly in the form of metal oxides or precipitated metal hydroxides and the bulk of this material is nonradioactive. One method being developed to pretreat this waste takes advantage of the amphoteric character of aluminum and other nonradioactive elements. Previous studies have reported on the dissolution of eleven elements from simulated sludge using NaOH solutions up to 6M. This work provides a comparative study using KOH. The effectiveness of the alkali washing as a treatment method to reduce the bulk of radioactive sludge requiring long term isolation will be discussed.

  16. An insight into liquid water networks through hydrogen bonding halide anion: Stimulated Raman scattering

    NASA Astrophysics Data System (ADS)

    Wang, Shenghan; Fang, Wenhui; Li, Tianyu; Li, Fangfang; Sun, Chenglin; Li, Zuowei; Huang, Yuxin; Men, Zhiwei

    2016-04-01

    We have studied the interaction between water molecules and halide anions and acquired the influence of concentration by the spontaneous Raman spectrum. The results agreed well with the previous researches. To explore further, the stimulated Raman scattering of a halide-water binary solution is measured to study the nature of the hydrogen bonding between water molecules and halogen anions. Under the effect of laser-induced plasma, the OH stretching vibration spectra of aqueous solutions of halogen ions pretty exhibit different trend compared with that of spontaneous Raman spectrum. The frequency shifts of water OH vibration show different values and directions with adding different halide anions. The red shift of F-- and Cl--water molecule clusters is due to the process of charge transfer, whereas the blue shift of Br-- and I--water molecule cluster is due to polarization effect without charge transfer. The results demonstrate that F- and Cl- slightly weaken the hydrogen bond (HB), whereas Br- and I- enhance HB in the water cluster. The decrease of concentration of halogen ions aqueous solution can weaken the effect on the HB.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. Bromine and heavy halide chemistry at the air/water and air/ice interfaces: a computational approach

    NASA Astrophysics Data System (ADS)

    Gladich, I.; Shepson, P. B.; Szleifer, I.; Carignano, M.

    2010-12-01

    The air-water and air-ice interfaces are critically important surfaces, with respect to the physical and chemical properties of the Earth's atmosphere. In particular chloride, bromide and iodide ions are strongly involved in the reactions occurring at aerosol surfaces that are hydrated and at the air-ice interface in the polar boundary layer. Unfortunately, experimental access to these interfaces are quite problematic and the computational approach, based on molecular dynamic simulations and quantum mechanic calculations, is an interesting alternative approach. In this work, molecular dynamic (MD) simulations are used to study the halide enhancements at the air-water interface in the case of a dilute mixture of iodide, bromide and chloride ions. The MD results show how the air- water halide enhancement is different in the case of mixtures from the case of binary solutions (i.e. anions plus counter-positive ions) and how the presence of these halides at the interfaces depends from their relative concentrations in solution. In detail, heavy halides are strongly enhanced at the interfaces even if they are minor constituents in the bulk. Furthermore the enhancement of the larger halide ions, like bromide, at the surface is greater if lighter halides, like chloride, are in greater excess in the bulk. The applications of this last result on some real system, like sea-water, and the importance of bromide ions in the polar chemistry of ozone depletion events suggest a combined approach, MD and quantum mechanism (QM) calculation, to investigate the ozonation reaction of bromide (Br-+O3 → BrO-+O2 ) in the ice-QLL and in bulk water. The study of the reaction constants suggests how the different environments can affect the kinetics of such reaction. These results can help to understand the complex chemistry occurring at the air-water interface of hydrated aerosol and at the air-ice interface in the polar boundary layer.

  3. Assesment of Alkali Resistance of Basalt Used as Concrete Aggregates

    NASA Astrophysics Data System (ADS)

    al-Swaidani, Aref M.; Baddoura, Mohammad K.; Aliyan, Samira D.; Choeb, Walid

    2015-11-01

    The objective of this paper is to report a part of an ongoing research on the influence of using crushed basalt as aggregates on one of durability-related properties of concrete (i.e. alkali-silica reaction which is the most common form of Alkali-Aggregate Reaction). Alkali resistance has been assessed through several methods specified in the American Standards. Results of petrographic examination, chemical test (ASTM C289) and accelerated mortar bar test (ASTM C1260) have particularly been reported. In addition, the weight change and compressive strength of 28 days cured concrete containing basaltic aggregates were also reported after 90 days of exposure to 10% NaOH solution. Dolomite aggregate were used in the latter test for comparison. The experimental results revealed that basaltic rocks quarried from As-Swaida'a region were suitable for production of aggregates for concrete. According to the test results, the studied basalt aggregates can be classified as innocuous with regard to alkali-silica reaction. Further, the 10% sodium hydroxide attack did not affect the compressive strength of concrete.

  4. 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.

  5. 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.

  6. Alkali-activated binders by use of industrial by-products

    SciTech Connect

    Buchwald, A.; Schulz, M

    2005-05-01

    Cement kiln dust (CKD) materials are used as alkaline accelerators for latent hydraulic substances and as alkali activators for different alumosilicate materials, including ground-granulated blast furnace slag, low-calcium fly ash and metakaolin. The dusts differ in their phase composition, especially in the amount of reactive phases and the kind and amount of alkali salts. The quantitative phase composition, pore solution composition and strength behavior of the activated blends is reported.

  7. 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.

  8. Precision optical metrology with alkali-atom isoclinic points

    NASA Astrophysics Data System (ADS)

    Wells, Nathan; Driskell, Travis; Camparo, James

    2016-06-01

    Vapour-phase spectroscopy rarely involves transitions between well-isolated atomic states. Routinely, the spectra comprise overlapped Doppler/pressure-broadened resonances, which leads to a “pulling” of the spectral peaks from their true atomic resonance frequencies. This pulling gives the absorption resonances a temperature sensitivity, which limits their utility for precision spectroscopy when sub-Doppler techniques are not viable. Here, we discuss the use of alkali isoclinic points as a solution to this problem.

  9. 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

  10. Bright light-emitting diodes based on organometal halide perovskite

    NASA Astrophysics Data System (ADS)

    Tan, Zhi-Kuang; Moghaddam, Reza Saberi; Lai, May Ling; Docampo, Pablo; Higler, Ruben; Deschler, Felix; Price, Michael; Sadhanala, Aditya; Pazos, Luis M.; Credgington, Dan; Hanusch, Fabian; Bein, Thomas; Snaith, Henry J.; Friend, Richard H.

    2014-09-01

    Solid-state light-emitting devices based on direct-bandgap semiconductors have, over the past two decades, been utilized as energy-efficient sources of lighting. However, fabrication of these devices typically relies on expensive high-temperature and high-vacuum processes, rendering them uneconomical for use in large-area displays. Here, we report high-brightness light-emitting diodes based on solution-processed organometal halide perovskites. We demonstrate electroluminescence in the near-infrared, green and red by tuning the halide compositions in the perovskite. In our infrared device, a thin 15 nm layer of CH3NH3PbI3-xClx perovskite emitter is sandwiched between larger-bandgap titanium dioxide (TiO2) and poly(9,9‧-dioctylfluorene) (F8) layers, effectively confining electrons and holes in the perovskite layer for radiative recombination. We report an infrared radiance of 13.2 W sr-1 m-2 at a current density of 363 mA cm-2, with highest external and internal quantum efficiencies of 0.76% and 3.4%, respectively. In our green light-emitting device with an ITO/PEDOT:PSS/CH3NH3PbBr3/F8/Ca/Ag structure, we achieved a luminance of 364 cd m-2 at a current density of 123 mA cm-2, giving external and internal quantum efficiencies of 0.1% and 0.4%, respectively. We show, using photoluminescence studies, that radiative bimolecular recombination is dominant at higher excitation densities. Hence, the quantum efficiencies of the perovskite light-emitting diodes increase at higher current densities. This demonstration of effective perovskite electroluminescence offers scope for developing this unique class of materials into efficient and colour-tunable light emitters for low-cost display, lighting and optical communication applications.

  11. The role of halide ions in the anisotropic growth of gold nanoparticles: a microscopic, atomistic perspective.

    PubMed

    Meena, Santosh Kumar; Celiksoy, Sirin; Schäfer, Philipp; Henkel, Andreas; Sönnichsen, Carsten; Sulpizi, Marialore

    2016-05-21

    We provide a microscopic view of the role of halides in controlling the anisotropic growth of gold nanorods through a combined computational and experimental study. Atomistic molecular dynamics simulations unveil that Br(-) adsorption is not only responsible for surface passivation, but also acts as the driving force for CTAB micelle adsorption and stabilization on the gold surface in a facet-dependent way. The partial replacement of Br(-) by Cl(-) decreases the difference between facets and the surfactant density. Finally, in the CTAC solution, no halides or micellar structures protect the gold surface and further gold reduction should be uniformly possible. Experimentally observed nanoparticle's growth in different CTAB/CTAC mixtures is more uniform and faster as the amount of Cl(-) increases, confirming the picture from the simulations. In addition, the surfactant layer thickness measured on nanorods exposed to CTAB and CTAC quantitatively agrees with the simulation results. PMID:27118188

  12. Ion pair complexes and anion binding in the solution of a ditopic receptor.

    PubMed

    Mäkelä, T; Rissanen, K

    2016-04-21

    The synthesis and crystal structures with alkali halides of a ditopic benzo-15-crown-5 bis-urea receptor have been presented. In addition, the anion binding properties of and its alkali metal complexes in solution are presented. A comprehensive single-crystal X-ray crystallographic study of , all together 13 crystal structures, including the ion pair complexes with NaCl, NaBr, NaI, KF, KCl, KBr, KI, RbF, RbCl, and RbI, give a detailed view of how behaves in the solid-state with different alkali halides depending on the size of the cation and anion. In the solid-state forms a 1 : 1 complex with a sodium cation and the anion is complexed as a contact (NaCl) or a separate ion pair (NaBr, NaI). With larger potassium and rubidium cations assembles into a 2 : 1 complex and forms a separated ion pair complex with the anion. Reflecting the crystal structures the forms a 1 : 1 complex with Na(+) in solution, and a 2 : 1 complex with K(+), which were verified by Job's plot analysis in 4 : 1 CDCl3/dimethyl sulfoxide. The binding strength of the monomeric [·Na](+) and the dimeric [2·K](+) toward chloride, bromide and iodide anions was studied by (1)H NMR titrations in 4 : 1 CDCl3/DMSO, and a clear turn-on effect of the cation complexation compared to the neutral receptor alone (Ka with for Cl(-), Br(-) and I(-) being 832, 174 and 32 M(-1), respectively) was observed. The monomeric [·Na](+) binds chloride 9, bromide 8, and iodide 12 times stronger than , while for the dimeric [2K](+) the corresponding increase in binding is 51 (Cl(-)), 84 (Br(-)), and 22 (I(-)) times with the same stoichiometric ratios as observed for the ion pair complexes in the solid-state. PMID:26953675

  13. 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.

  14. 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.

  15. Nanowire Lasers of Formamidinium Lead Halide Perovskites and Their Stabilized Alloys with Improved Stability.

    PubMed

    Fu, Yongping; Zhu, Haiming; Schrader, Alex W; Liang, Dong; Ding, Qi; Joshi, Prakriti; Hwang, Leekyoung; Zhu, X-Y; Jin, Song

    2016-02-10

    The excellent intrinsic optoelectronic properties of methylammonium lead halide perovskites (MAPbX3, X = Br, I), such as high photoluminescence quantum efficiency, long carrier lifetime, and high gain coupled with the facile solution growth of nanowires make them promising new materials for ultralow-threshold nanowire lasers. However, their photo and thermal stabilities need to be improved for practical applications. Herein, we report a low-temperature solution growth of single crystal nanowires of formamidinium lead halide perovskites (FAPbX3) that feature red-shifted emission and better thermal stability compared to MAPbX3. We demonstrate optically pumped room-temperature near-infrared (∼820 nm) and green lasing (∼560 nm) from FAPbI3 (and MABr-stabilized FAPbI3) and FAPbBr3 nanowires with low lasing thresholds of several microjoules per square centimeter and high quality factors of about 1500-2300. More remarkably, the FAPbI3 and MABr-stabilized FAPbI3 nanowires display durable room-temperature lasing under ∼10(8) shots of sustained illumination of 402 nm pulsed laser excitation (150 fs, 250 kHz), substantially exceeding the stability of MAPbI3 (∼10(7) laser shots). We further demonstrate tunable nanowire lasers in wider wavelength region from FA-based lead halide perovskite alloys (FA,MA)PbI3 and (FA,MA)Pb(I,Br)3 through cation and anion substitutions. The results suggest that formamidinium lead halide perovskite nanostructures could be more promising and stable materials for the development of light-emitting diodes and continuous-wave lasers. PMID:26727024

  16. In-Situ Investigation of Tomato Plants as Methyl Halide Sources

    NASA Astrophysics Data System (ADS)

    King, D. B.; Butler, J. H.; Mondeel, D. J.

    2002-05-01

    Natural halocarbons contribute significantly to the destruction of stratospheric ozone. Methyl bromide and methyl chloride, both of which come primarily from natural sources, supply about one-quarter of the equivalent chlorine to the stratosphere. Other halogenated compounds, such as dibromomethane, bromoform, and methyl iodide, might be significant halogen sources to the stratosphere as well. The budgets of these compounds, and the mechanisms responsible for their production and destruction, generally are poorly understood. For example, known sources of both methyl bromide and methyl chloride outweigh their known sinks by 50-100%, making it difficult to predict future atmospheric concentrations of these compounds. As the global climate changes, atmospheric halocarbon concentrations are likely to respond to changes in sea surface temperature, biological productivity on land and in water, and global wind patterns. Terrestrial plants are a potentially significant source of many light halocarbons. As a first cut to assess this potential, we measured the production of about 20 halocarbons by tomato plants in a hydroponic greenhouse in Northern California. This enabled us to investigate production directly from the plants, without the interference of soils, which have been shown to remove some of these compounds from the atmosphere. Results differed for the methyl halides and the polyhalogenated compounds. Methyl halide production was small or zero during initial experiments. However, the addition of a halide ion solution (KBr, KCl, and KI) to the plants' nutrient mixture appeared to increase production of methyl bromide (by a factor of three) and methyl iodide (by a factor of seven) significantly. In contrast, several polyhalogenated compounds (e.g., bromoform and bromochloromethane) were produced during all experiments, with increases on the order of 50% to 600%. The addition of the halide solution did not affect the production of these compounds. The results from

  17. Lithological influence of aggregate in the alkali-carbonate reaction

    SciTech Connect

    Lopez-Buendia, A.M. . E-mail: angel.lopez@aidico.es; Climent, V. . E-mail: vcliment@grupogla.com; Verdu, P.

    2006-08-15

    The reactivity of carbonate rock with the alkali content of cement, commonly called alkali-carbonate reaction (ACR), has been investigated. Alkali-silica reaction (ASR) can also contribute in the alkali-aggregate reaction (AAR) in carbonate rock, mainly due to micro- and crypto-crystalline quartz or clay content in carbonate aggregate. Both ACR and ASR can occur in the same system, as has been also evidenced on this paper. Carbonate aggregate samples were selected using lithological reactivity criteria, taking into account the presence of dedolomitization, partial dolomitization, micro- and crypto-crystalline quartz. Selected rocks include calcitic dolostone with chert (CDX), calcitic dolostone with dedolomitization (CDD), limestone with chert (LX), marly calcitic dolostone with partial dolomitization (CD), high-porosity ferric dolostone with clays (FD). To evaluate the reactivity, aggregates were studied using expansion tests following RILEM AAR-2, AAR-5, a modification using LiOH AAR-5Li was also tested. A complementary study was done using petrographic monitoring with polarised light microscopy on aggregates immersed in NaOH and LiOH solutions after different ages. SEM-EDAX has been used to identify the presence of brucite as a product of dedolomitization. An ACR reaction showed shrinkage of the mortar bars in alkaline solutions explained by induced dedolomitization, while an ASR process typically displayed expansion. Neither shrinkage nor expansion was observed when mortar bars were immersed in solutions of lithium hydroxide. Carbonate aggregate classification with AAR pathology risk has been elaborated based on mechanical behaviours by expansion and shrinkage. It is proposed to be used as a petrographic method for AAR diagnosis to complement the RILEM AAR1 specifically for carbonate aggregate. Aggregate materials can be classified as I (non-reactive), II (potentially reactive), and III (probably reactive), considering induced dedolomitization ACR

  18. 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.

  19. [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

  20. 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

  1. 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.

  2. 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

  3. Spectral Features and Charge Dynamics of Lead Halide Perovskites: Origins and Interpretations.

    PubMed

    Sum, Tze Chien; Mathews, Nripan; Xing, Guichuan; Lim, Swee Sien; Chong, Wee Kiang; Giovanni, David; Dewi, Herlina Arianita

    2016-02-16

    Lead halide perovskite solar cells are presently the forerunner among the third generation solution-processed photovoltaic technologies. With efficiencies exceeding 20% and low production costs, they are prime candidates for commercialization. Critical insights into their light harvesting, charge transport, and loss mechanisms have been gained through time-resolved optical probes such as femtosecond transient absorption spectroscopy (fs-TAS), transient photoluminescence spectroscopy, and time-resolved terahertz spectroscopy. Specifically, the discoveries of long balanced electron-hole diffusion lengths and gain properties in halide perovskites underpin their significant roles in uncovering structure-function relations and providing essential feedback for materials development and device optimization. In particular, fs-TAS is becoming increasingly popular in perovskite characterization studies, with commercial one-box pump-probe systems readily available as part of a researcher's toolkit. Although TAS is a powerful probe in the study of charge dynamics and recombination mechanisms, its instrumentation and data interpretation can be daunting even for experienced researchers. This issue is exacerbated by the sensitive nature of halide perovskites where the kinetics are especially susceptible to pump fluence, sample preparation and handling and even degradation effects that could lead to disparate conclusions. Nonetheless, with end-users having a clear understanding of TAS's capabilities, subtleties, and limitations, cutting-edge work with deep insights can still be performed using commercial setups as has been the trend for ubiquitous spectroscopy instruments like absorption, fluorescence, and transient photoluminescence spectrometers. Herein, we will first briefly examine the photophysical processes in lead halide perovskites, highlighting their novel properties. Next, we proceed to give a succinct overview of the fundamentals of pump-probe spectroscopy in relation

  4. Crystal growth of sulfide materials from alkali polysulfide liquids

    NASA Technical Reports Server (NTRS)

    White, W. B.

    1979-01-01

    The fluids experiment system was designed for low temperature solution growth, nominally aqueous solution growth. The alkali polysulfides, compositions in the systems Na2S-S and K2S-S form liquids in the temperature range of 190 C to 400 C. These can be used as solvents for other important classes of materials such as transition metal and other sulfides which are not soluble in aqueous media. Among these materials are luminescent and electroluminescent crystals whose physical properties are sensitive functions of crystal perfection and which could, therefore, serve as test materials for perfection improvement under microgravity conditions.

  5. PREPARATION OF URANIUM-ALUMINUM ALLOYS

    DOEpatents

    Moore, R.H.

    1962-09-01

    A process is given for preparing uranium--aluminum alloys from a solution of uranium halide in an about equimolar molten alkali metal halide-- aluminum halide mixture and excess aluminum. The uranium halide is reduced and the uranium is alloyed with the excess aluminum. The alloy and salt are separated from each other. (AEC)

  6. 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...

  7. 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...

  8. 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...

  9. 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

  10. 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.

  11. 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

  12. 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.

  13. High-Efficiency Light-Emitting Diodes of Organometal Halide Perovskite Amorphous Nanoparticles.

    PubMed

    Xing, Jun; Yan, Fei; Zhao, Yawen; Chen, Shi; Yu, Huakang; Zhang, Qing; Zeng, Rongguang; Demir, Hilmi Volkan; Sun, Xiaowei; Huan, Alfred; Xiong, Qihua

    2016-07-26

    Organometal halide perovskite has recently emerged as a very promising family of materials with augmented performance in electronic and optoelectronic applications including photovoltaic devices, photodetectors, and light-emitting diodes. Herein, we propose and demonstrate facile solution synthesis of a series of colloidal organometal halide perovskite CH3NH3PbX3 (X = halides) nanoparticles with amorphous structure, which exhibit high quantum yield and tunable emission from ultraviolet to near-infrared. The growth mechanism and photoluminescence properties of the perovskite amorphous nanoparticles were studied in detail. A high-efficiency green-light-emitting diode based on amorphous CH3NH3PbBr3 nanoparticles was demonstrated. The perovskite amorphous nanoparticle-based light-emitting diode shows a maximum luminous efficiency of 11.49 cd/A, a power efficiency of 7.84 lm/W, and an external quantum efficiency of 3.8%, which is 3.5 times higher than that of the best colloidal perovskite quantum-dot-based light-emitting diodes previously reported. Our findings indicate the great potential of colloidal perovskite amorphous nanoparticles in light-emitting devices. PMID:27284993

  14. Detection of halide ions with AlGaN /GaN high electron mobility transistors

    NASA Astrophysics Data System (ADS)

    Kang, B. S.; Ren, F.; Kang, M. C.; Lofton, C.; Tan, Weihong; Pearton, S. J.; Dabiran, A.; Osinsky, A.; Chow, P. P.

    2005-04-01

    AlGaN /GaN high electron mobility transistors (HEMTs) both with and without a Au gate are found to exhibit significant changes in channel conductance upon exposing the gate region to various halide ions. The polar nature of the halide ions leads to a change of surface charge in the gate region on the HEMT, producing a change in the surface potential at the semiconductor/liquid interface. HEMTs with a Au-gate electrode not only doubled the sensitivity of changing the channel conductance as compared to gateless HEMT, but also showed the opposite conductance behavior. When anions adsorbed on the Au, they produced a counter charge for electrovalence. These anions drag some counter ions from the bulk solution or create an image positive charge on the metal for the required neutrality. The gateless HEMTs can be used as sensors for a range of chemicals through appropriate modification with covalently bonded halide functional groups on the Au surface. This creates many possibilities to functionalize the surface for a wide range of integrated biological, chemical, and fluid monitoring sensors.

  15. Lead halide perovskite nanowire lasers with low lasing thresholds and high quality factors.

    PubMed

    Zhu, Haiming; Fu, Yongping; Meng, Fei; Wu, Xiaoxi; Gong, Zizhou; Ding, Qi; Gustafsson, Martin V; Trinh, M Tuan; Jin, Song; Zhu, X-Y

    2015-06-01

    The remarkable performance of lead halide perovskites in solar cells can be attributed to the long carrier lifetimes and low non-radiative recombination rates, the same physical properties that are ideal for semiconductor lasers. Here, we show room-temperature and wavelength-tunable lasing from single-crystal lead halide perovskite nanowires with very low lasing thresholds (220 nJ cm(-2)) and high quality factors (Q ∼ 3,600). The lasing threshold corresponds to a charge carrier density as low as 1.5 × 10(16) cm(-3). Kinetic analysis based on time-resolved fluorescence reveals little charge carrier trapping in these single-crystal nanowires and gives estimated lasing quantum yields approaching 100%. Such lasing performance, coupled with the facile solution growth of single-crystal nanowires and the broad stoichiometry-dependent tunability of emission colour, makes lead halide perovskites ideal materials for the development of nanophotonics, in parallel with the rapid development in photovoltaics from the same materials. PMID:25849532

  16. Communication: Modeling of concentration dependent water diffusivity in ionic solutions: Role of intermolecular charge transfer

    SciTech Connect

    Yao, Yi; Berkowitz, Max L. E-mail: ykanai@unc.edu; Kanai, Yosuke E-mail: ykanai@unc.edu

    2015-12-28

    The translational diffusivity of water in solutions of alkali halide salts depends on the identity of ions, exhibiting dramatically different behavior even in solutions of similar salts of NaCl and KCl. The water diffusion coefficient decreases as the salt concentration increases in NaCl. Yet, in KCl solution, it slightly increases and remains above bulk value as salt concentration increases. Previous classical molecular dynamics simulations have failed to describe this important behavior even when polarizable models were used. Here, we show that inclusion of dynamical charge transfer among water molecules produces results in a quantitative agreement with experiments. Our results indicate that the concentration-dependent diffusivity reflects the importance of many-body effects among the water molecules in aqueous ionic solutions. Comparison with quantum mechanical calculations shows that a heterogeneous and extended distribution of charges on water molecules around the ions due to ion-water and also water-water charge transfer plays a very important role in controlling water diffusivity. Explicit inclusion of the charge transfer allows us to model accurately the difference in the concentration-dependent water diffusivity between Na{sup +} and K{sup +} ions in simulations, and it is likely to impact modeling of a wide range of systems for medical and technological applications.

  17. Communication: Modeling of concentration dependent water diffusivity in ionic solutions: Role of intermolecular charge transfer

    NASA Astrophysics Data System (ADS)

    Yao, Yi; Berkowitz, Max L.; Kanai, Yosuke

    2015-12-01

    The translational diffusivity of water in solutions of alkali halide salts depends on the identity of ions, exhibiting dramatically different behavior even in solutions of similar salts of NaCl and KCl. The water diffusion coefficient decreases as the salt concentration increases in NaCl. Yet, in KCl solution, it slightly increases and remains above bulk value as salt concentration increases. Previous classical molecular dynamics simulations have failed to describe this important behavior even when polarizable models were used. Here, we show that inclusion of dynamical charge transfer among water molecules produces results in a quantitative agreement with experiments. Our results indicate that the concentration-dependent diffusivity reflects the importance of many-body effects among the water molecules in aqueous ionic solutions. Comparison with quantum mechanical calculations shows that a heterogeneous and extended distribution of charges on water molecules around the ions due to ion-water and also water-water charge transfer plays a very important role in controlling water diffusivity. Explicit inclusion of the charge transfer allows us to model accurately the difference in the concentration-dependent water diffusivity between Na+ and K+ ions in simulations, and it is likely to impact modeling of a wide range of systems for medical and technological applications.

  18. 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.

  19. 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.

  20. 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.

  1. Photophysics of Hybrid Lead Halide Perovskites: The Role of Microstructure.

    PubMed

    Srimath Kandada, Ajay Ram; Petrozza, Annamaria

    2016-03-15

    Since the first reports on high efficiency, solution processed solar cells based on hybrid lead halide perovskites, there has been an explosion of activities on these materials. Researchers with interests spanning the full range from conventional inorganic to emerging organic and hybrid optoelectronic technologies have been contributing to the prolific research output. This has led to solar cell power conversion efficiencies now exceeding 20% and the demonstration of proofs of concept for electroluminescent and lasing devices. Hybrid perovskites can be self-assembled by a simple chemical deposition of the constituent units, with the possibility of integrating the useful properties of organic and inorganic compounds at the molecular scale within a single crystalline material, thus enabling a fine-tuning of the electronic properties. Tellingly, the fundamental properties of these materials may make us think of a new, solution processable, GaAs-like semiconductor. While this can be true to a first approximation, hybrid perovskites are intrinsically complex materials, where the presence of various types of interactions and structural disorder may strongly affect their properties. In particular, a clear understanding and control of the relative interactions between the organic and inorganic moieties is of paramount importance to properly disentangle their innate physics. In this Account 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 the 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 luminescence properties of the semiconductor. Finally 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

  2. 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.

  3. 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.

  4. 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

  5. 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

  6. 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

  7. The Interfacial Transition Zone in Alkali-Activated Slag Mortars

    NASA Astrophysics Data System (ADS)

    San Nicolas, Rackel; Provis, John

    2015-12-01

    The interfacial transition zone (ITZ) is known to strongly influence the mechanical and transport properties of mortars and concretes. This paper studies the ITZ between siliceous (quartz) aggregates and alkali activated slag binders in the context of mortar specimens. Backscattered electron images (BSE) generated in an environmental scanning electron microscope (ESEM) are used to identify unreacted binder components, reaction products and porosity in the zone surrounding aggregate particles, by composition and density contrast. X-ray mapping is used to exclude the regions corresponding to the aggregates from the BSE image of the ITZ, thus enabling analysis of only the binder phases, which are segmented into binary images by grey level discrimination. A distinct yet dense ITZ region is present in the alkali-activated slag mortars, containing a reduced content of unreacted slag particles compared to the bulk binder. The elemental analysis of this region shows that it contains a (C,N)-A-S-H gel which seems to have a higher content of Na (potentially deposited through desiccation of the pore solution) and a lower content of Ca than the bulk inner and outer products forming in the main binding region. These differences are potentially important in terms of long-term concrete performance, as the absence of a highly porous interfacial transition zone region is expected to provide a positive influence on the mechanical and transport properties of alkali-activated slag concretes.

  8. Effect of alkali treatment on surface morphology of titanium

    SciTech Connect

    Tan, K. J. Wahab, M. A. A. Mahmod, S. Idris, M. I. Abdullah, H. Z.

    2015-07-22

    Alkali and heat treatments were first introduced by Kim et al. to prepare a bioactive surface on titanium. This method has been proven very effective and widely used in other studies to promote titanium osteointegration. This study aims to investigate further the effect of alkali treatment on surface morphology of high purity titanium. High purity titanium foils were immersed in NaOH aqueous solutions of 0.5 M, 5 M and 15 M at 60°C and 80 °C for 1, 3 and 7 days. The surface morphology was examined using Field Emission Scanning Electron Microscope (FESEM). The obtained phases were analysed using Fourier Transform Infrared Spectroscopy (FTIR) in the spectra range of 4000-600 cm{sup −1} at 4 cm{sup −1} resolution and 50 scans. At the same soaking temperature and soaking time, a thicker porous network was observed with increasing concentration of NaOH. At the same soaking temperature, a much porous structure was observed with increasing soaking time. At constant alkali concentration, more homogenously distributed porous surface structure was observed with increasing soaking temperature.

  9. The effects of potassium and rubidium hydroxide on the alkali-silica reaction

    SciTech Connect

    Shomglin, K.; Turanli, L.; Wenk, H.-R.; Monteiro, P.J.M.; Sposito, G

    2003-11-01

    Expansion of mortar specimens prepared with an aggregate of mylonite from the Santa Rosa mylonite zone in southern California was studied to investigate the effect of different alkali ions on the alkali-silica reaction in concrete. The expansion tests indicate that mortar has a greater expansion when subjected to a sodium hydroxide bath than in a sodium-potassium-rubidium hydroxide bath. Electron probe microanalysis (EPMA) of mortar bars at early ages show that rubidium ions, used as tracer, were present throughout the sample by the third day of exposure. The analysis also shows a high concentration of rubidium in silica gel from mortar bars exposed to bath solutions containing rubidium. The results suggest that expansion of mortar bars using ASTM C 1260 does not depend on the diffusion of alkali ions. The results indicate that the expansion of alkali-silica gel depends on the type of alkali ions present. Alkali-silica gel containing rubidium shows a lower concentration of calcium, suggesting competition for the same sites.

  10. 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.

  11. Process for extracting technetium from alkaline solutions

    DOEpatents

    Moyer, Bruce A.; Sachleben, Richard A.; Bonnesen, Peter V.

    1995-01-01

    A process for extracting technetium values from an aqueous alkaline solution containing at least one alkali metal hydroxide and at least one alkali metal nitrate, the at least one alkali metal nitrate having a concentration of from about 0.1 to 6 molar. The solution is contacted with a solvent consisting of a crown ether in a diluent for a period of time sufficient to selectively extract the technetium values from the aqueous alkaline solution. The solvent containing the technetium values is separated from the aqueous alkaline solution and the technetium values are stripped from the solvent.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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

  17. Effects of halides on reaction of nucleosides with ozone.

    PubMed

    Suzuki, Toshinori; Kaya, Eriko; Inukai, Michiyo

    2012-01-01

    Ozone (O(3)), a major component of photochemical oxidants, is used recently as a deodorizer in living spaces. It has been reported that O(3) can directly react with DNA, causing mutagenesis in human cells and carcinogenesis in mice. However, little is known about the effects of coexistent ions in the reaction of O(3). In the present study, we analyzed the effects of halides on the reaction of O(3) with nucleosides using reversed-phase high-performance liquid chromatography with ultraviolet detection. When aqueous O(3) solution was added to a nucleoside mixture in potassium phosphate buffer (pH 7.3), the nucleosides were consumed with the following decreasing order of importance: dGuo > Thd > dCyd > dAdo. The effects of addition of fluoride and chloride in the system were slight. Bromide suppressed the reactions of dGuo, Thd, and dAdo but enhanced the reaction of dCyd. The major products were 5-hydroxy-2'-deoxycytidine, 5-bromo-2'-deoxycytidine, and 8-bromo-2'-deoxyguanosine. The time course and pH dependence of the product yield indicated formation of hypobromous acid as the reactive agent. Iodide suppressed all the reactions effectively. The results suggest that bromide may alter the mutation spectrum by O(3) in humans. PMID:22646086

  18. Spectroscopic imaging of metal halide high-intensity discharge lamps

    NASA Astrophysics Data System (ADS)

    Bonvallet, Geoffrey A.

    The body of this work consists of three main research projects. An optical- and near-ultraviolet-wavelength absorption study sought to determine absolute densities of ground and excited level Sc atoms, ground level Sc + ions, and ground level Na atoms in a commercial 250 W metal halide high intensity discharge lamp during operation. These measurements also allowed the determination of the arc temperature and absolute electron density as functions of radius. Through infrared emission spectroscopy, relative densities of sodium and scandium were determined as functions of radius. Using the absolute densities gained from the optical experiment, these relative densities were calibrated. In addition, direct observation of the infrared emission allowed us to characterize the infrared power losses of the lamp. When considered as a fraction of the overall power consumption, the near-infrared spectral power losses were not substantial enough to warrant thorough investigation of their reduction in these lamps. The third project was an attempt to develop a portable x-ray diagnostic experiment. Two-dimensional spatial maps of the lamps were analyzed to determine absolute elemental mercury densities and the arc temperature as a function of radius. Two methods were used to improve the calibration of the density measurements and to correct for the spread in x-ray energy: known solutions of mercury in nitric acid, and an arc lamp which was uniformly heated to evaporate the mercury content. Although many complexities arose in this experiment, its goal was successfully completed.

  19. A study of the influence of halide adsorption on a reconstructed Au(111) electrode by second harmonic generation

    NASA Astrophysics Data System (ADS)

    Friedrich, A.; Shannon, C.; Pettinger, B.

    1991-07-01

    Optical second harmonic generation (SHG) rotational anisotropy measurements were employed to study the influence of specifically adsorbed anions on the reconstructed Au(111)-(1 × 23) surface. Azimuthal rotation of the gold electrode at different potentials yields for the unreconstructed Au(111)-(1 × 1) surface the well-known three-fold symmetry pattern, while for the reconstructed Au(111)-(1 × 23) an additional one-fold symmetry pattern is observed, which leads to an assignment of Cs-symmetry for this surface. Due to the observation of this symmetry change Cs → C3v it is possible to monitor in situ the reversible transition between Au(111)-(1 × 23) and Au(111)-(1 × 1). While in perclorate solution the phase transition occurs over a wide potential region, in halide containing solution the same phase transition is restricted to the sharp potential region typical for the halide adsorption.

  20. 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

  1. Self-regulation mechanism for charged point defects in hybrid halide perovskites

    DOE PAGESBeta

    Walsh, Aron; Scanlon, David O.; Chen, Shiyou; Gong, X. G.; Wei, Su -Huai

    2014-12-11

    Hybrid halide perovskites such as methylammonium lead iodide (CH3NH3PbI3) exhibit unusually low free-carrier concentrations despite being processed at low-temperatures from solution. We demonstrate, through quantum mechanical calculations, that an origin of this phenomenon is a prevalence of ionic over electronic disorder in stoichiometric materials. Schottky defect formation provides a mechanism to self-regulate the concentration of charge carriers through ionic compensation of charged point defects. The equilibrium charged vacancy concentration is predicted to exceed 0.4 % at room temperature. Furthermore, this behavior, which goes against established defect conventions for inorganic semiconductors, has implications for photovoltaic performance.

  2. Research on mouse model of grade II corneal alkali burn

    PubMed Central

    Bai, Jun-Qiang; Qin, Hai-Feng; Zhao, Shi-Hong

    2016-01-01

    AIM To choose appropriate concentration of sodium hydroxide (NaOH) solution to establish a stable and consistent corneal alkali burn mouse model in grade II. METHODS The mice (n=60) were randomly divided into four groups and 15 mice each group. Corneal alkali burns were induced by placing circle filter paper soaked with NaOH solutions on the right central cornea for 30s. The concentrations of NaOH solutions of groups A, B, C, and D were 0.1 mol/L, 0.15 mol/L, 0.2 mol/L, and 1.0 mol/L respectively. Then these corneas were irrigated with 20 mL physiological saline (0.9% NaCl). On day 7 postburn, slit lamp microscope was used to observe corneal opacity, corneal epithelial sodium fluorescein staining positive rate, incidence of corneal ulcer and corneal neovascularization, meanwhile pictures of the anterior eyes were taken. Cirrus spectral domain optical coherence tomography was used to scan cornea to observe corneal epithelial defect and corneal ulcer. RESULTS Corneal opacity scores (x±s) were not significantly different between the group A and group B (P=0.097). Incidence of corneal ulcer in group B was significantly higher than that in group A (P=0.035). Incidence of corneal ulcer and perforation rate in group B was lower than that in group C. Group C and D had corneal neovascularization, and incidence of corneal neovascularization in group D was significantly higher than that in group C (P=0.000). CONCLUSION Using 0.15 mol/L NaOH can establish grade II mouse model of corneal alkali burns. PMID:27162717

  3. Molecular dynamics simulations of the surface tension and structure of salt solutions and clusters.

    PubMed

    Sun, Lu; Li, Xin; Hede, Thomas; Tu, Yaoquan; Leck, Caroline; Ågren, Hans

    2012-03-15

    Sodium halides, which are abundant in sea salt aerosols, affect the optical properties of aerosols and are active in heterogeneous reactions that cause ozone depletion and acid rain problems. Interfacial properties, including surface tension and halide anion distributions, are crucial issues in the study of the aerosols. We present results from molecular dynamics simulations of water solutions and clusters containing sodium halides with the interatomic interactions described by a conventional force field. The simulations reproduce experimental observations that sodium halides increase the surface tension with respect to pure water and that iodide anions reach the outermost layer of water clusters or solutions. It is found that the van der Waals interactions have an impact on the distribution of the halide anions and that a conventional force field with optimized parameters can model the surface tension of the salt solutions with reasonable accuracy. PMID:22352372

  4. 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.

  5. Laboratory investigation of combination of alkali/surfactant/polymer technology for Daqing EOR

    SciTech Connect

    Gao Shutang; Li Huabin; Li Hongfu

    1995-08-01

    Alkali/surfactant/polymer (ASP) formulas were developed for the Daqing oil field, Peoples Republic of China, with two surfactants from the US (Petrostep B-100 and a blend of TRS-18 and TRS-40) and one Chinese surfactant (PS-D{sub 2}). Each ASP solution gave interfacial tension (IFT) values in the range of 1 {times} 10{sup {minus}3} mN/m. Rheologic studies with polyacrylamide polymers indicate that solution viscosity decreases with alkali addition, as does the pseudoplasticity of the solution. Addition of surfactant to the alkali/polymer solution increases the solution viscosity with no slope change in the viscosity-vs.-shear-rate plot. Incremental oil recovery was higher than that with waterflood; 20% original oil in place (OOIP) for 0.2-PV ASP injection and 33% OOIP for 0.3-PV ASP injection in Daqing core. Surfactant and alkali retention were both < 1 mg/g sand. The positive results of this laboratory study provided a fluid formula for a pilot ASP flood in the Daqing oil field.

  6. Determination of Alkali Ions in Biological and Environmental Samples.

    PubMed

    Hauser, Peter C

    2016-01-01

    An overview of the common methods for the determination of the alkali metals is given. These are drawn from all of the three principle branches of quantitative analysis and consist mainly of optical atomic spectrometric methods, ion-selective electrodes, and the separation methods of ion-chromatography and capillary electrophoresis. Their main characteristics and performance parameters are discussed. Important specific applications are also examined, namely clinical analysis, single cell analysis, the analysis of soil samples and hydroponic nutrient solutions, as well as the detection of the radioactive (137)Cs isotope. PMID:26860298

  7. 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.

  8. 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.

  9. Calorimetric and theoretical study of the interaction between some saccharides and sodium halide in water.

    PubMed

    Zhuo, Kelei; Fu, Yingyi; Bai, Guangyue; Wang, Jianji; Yan, Haike; Wang, Hanqing

    2012-08-23

    Dilution enthalpies and mixing enthalpies of sodium halide and some saccharides (glucose, galactose, xylose, arabinose, fructose, and sucrose) in aqueous solution were determined by calorimetric measurements at 298.15 K. The values were used to determine enthalpic pair interaction parameters. Combined with Gibbs energy pair parameters, entropic pair interaction parameters were also obtained. Theoretical calculations at the B3LYP/6-311++G(d,p) level were carried out to provide the information of structures and thermodynamic functions. The information reveals the thermodynamic essence of the interactions between sodium halide and saccharides in aqueous solutions. The experimental results and theoretical calculations show that the sign of enthalpic pair interaction parameter 2υh(ES) is determined by the direct interaction between saccharides and ions, whereas the difference in value of 2υh(ES) for different saccharides or electrolytes depends on the partial dehydration of saccharides or anions in aqueous solution. The difference in value of entropic pair interaction parameters depends partly on the different dominant interactions in the process of partial dehydration of saccharides or ions. An enthalpy-entropy compensation relationship was observed for the sodium bromide-aldopyranose-water systems. Remarkably, it can be conjectured that the hydration entropy of glucose is lower than for other monosaccharides. Perhaps it is one of the reasons why glucose plays an important role in living organisms rather than other monosaccharides. PMID:22779908

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. Photoinduced electron transfer double fragmentation. An oxygen-mediated radical chain process in the cofragmentation of aminopinacol donors with organic halides

    SciTech Connect

    Chen, L.; Farahat, M.S.; Gan, H.; Whitten, D.G.; Farid, S. |

    1995-06-14

    We reprot an investigation in which excited states of amino pinacols 1-3 are reacted with the halides CCl{sub 4}, benzyl bromide, and p-cyanobenzyl bromide. Interesting results from this study include the finding that low-to-moderate quantum efficiencies for reaction are observed when the reactions are carried out under degassed conditions, indicating that the halide radical anions must survive long enough within the initial ion pair formed in the quenching step to undergo considerable return electron transfer. More strikingly we find that for certain pinacol-halide combinations reaction in aerared solutions leads to much higher efficiencies, which can be attributed to a chain reaction involving oxygen capture of a primary radical product. 25 refs., 1 fig., 1 tab.

  15. 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.

  16. 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

  17. Concentration Effects and Ion Properties Controlling the Fractionation of Halides in Sea Spray

    NASA Astrophysics Data System (ADS)

    Guzman, M. I.; Pillar, E. A.

    2013-12-01

    During the aerosolization process at the sea surface, halides are incorporated into aerosol droplets, where they may play an important role in tropospheric ozone chemistry. Although this process may significantly contribute to the formation of reactive gas phase molecular halogens, little is known about the environmental factors that control how halides selectively accumulate at the air-water interface. In this study, the production of sea spray aerosol is simulated using electrospray ionization (ESI) of 100 nM equimolar solutions of NaCl, NaBr, NaI, NaNO2, NaNO3, NaClO4, and NaIO4. The microdroplets generated are analyzed by mass spectrometry to study the comparative enrichment of anions (fX-) and their correlation with ion properties. Although no correlation exists between fX- and the limiting equivalent ionic conductivity, the correlation coefficient of the linear fit with the size of the anions, dehydration free-energy, and polarizability α, is larger for the reciprocal square of anion size. The same pure physical process is observed in H2O and D2O. The factor fX- does not change with pH (6.8-8.6), counterion (Li+, Na+, K+, and Cs+) substitution effects, or solvent polarity changes in methanol- and ethanol-water mixtures (0 ≤ xwater ≤ 1). Polysorbate 20 surfactant is used to modify the structure of the interface. Despite the observed enrichment of I- on the air-water interface of equimolar solutions, our results of seawater mimic samples agree with a model in which the interfacial composition is increasingly enriched in I- < Br- < Cl- over the oceanic boundary layer due to concentration effects in sea spray aerosol formation. Experiments reporting the products for the ozonolysis of halides in microdroplets at typical ozone concentrations of ~ 50 ppbv display the formation or reactive halogen species that contribute to the destruction of ozone over the open ocean.

  18. 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.

  19. 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.

  20. 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

  1. Ab initio modeling of the optical properties in organometallic halide perovskites for photovoltaic applications

    NASA Astrophysics Data System (ADS)

    Neukirch, Amanda; Nei, Wanyi; Pedesseau, Laurent; Even, Jacky; Katan, Claudine; Mohite, Aditya; Tretiak, Segrei

    2015-03-01

    The need for an inexpensive, clean, and plentiful source of energy has generated large amounts of research in an assortment of solution processed organic and hybrid organic-inorganic solar cells. A relative newcomer to the field of solution processed photovoltaics is the lead halide perovskite solar cell. In the past 5 years, the efficiencies of devices made from this material have increased from 3.5% to nearly 20%. Despite the rapid development of organic-inorganic perovskite solar cells, a thorough understanding of the fundamental photophysical processes driving the high performance of these devices is not well understood. I am using state-of-the-art ab initio computational techniques in order to characterize the properties at the interface of perovskite devices in order to aide in materials design and device engineering. I will present an in-depth analysis of the electronic and optical properties of bulk and surface states of pure and mixed halide systems. The high-level static quantum mechanical calculations, including spin-orbit-coupling and the many body GW approach, identify the key electronic states involved in photoinduced dynamics. This knowledge provides important information on how the optical properties change with variations to the system. Supported by the DOE, the LANL LDRD program XW11, and CNLS.

  2. 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.

  3. 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

  4. 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

  5. Single Cesium Lead Halide Perovskite Nanocrystals at Low Temperature: Fast Single-Photon Emission, Reduced Blinking, and Exciton Fine Structure

    PubMed Central

    2016-01-01

    Metal-halide semiconductors with perovskite crystal structure are attractive due to their facile solution processability, and have recently been harnessed very successfully for high-efficiency photovoltaics and bright light sources. Here, we show that at low temperature single colloidal cesium lead halide (CsPbX3, where X = Cl/Br) nanocrystals exhibit stable, narrow-band emission with suppressed blinking and small spectral diffusion. Photon antibunching demonstrates unambiguously nonclassical single-photon emission with radiative decay on the order of 250 ps, representing a significant acceleration compared to other common quantum emitters. High-resolution spectroscopy provides insight into the complex nature of the emission process such as the fine structure and charged exciton dynamics. PMID:26771336

  6. Facile Precursor for Synthesis of Silver Nanoparticles Using Alkali Treated Maize Starch

    PubMed Central

    El-Rafie, M. H.; Ahmed, Hanan B.; Zahran, M. K.

    2014-01-01

    Silver nanoparticles were prepared by using alkali treated maize starch which plays a dual role as reducer for AgNO3 and stabilizer for the produced AgNPs. The redox reaction which takes a place between AgNO3 and alkali treated starch was followed up and controlled in order to obtain spherical shaped silver nanoparticles with mean size 4–6 nm. The redox potentials confirmed the principle role of alkali treatment in increasing the reducibility of starch macromolecules. The measurements of reducing sugars at the end of reaction using dinitrosalicylic acid reagent (DNS) were carried out in order to control the chemical reduction reaction. The UV/Vis spectra show that an absorption peak, occurring due to surface plasmon resonance (SPR), exists at 410 nm, which is characteristic to yellow color of silver nanoparticles solution. The samples have been characterized by transmission electron microscopy (TEM), which reveal the nanonature of the particles.

  7. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  9. Visualization of alkali-denatured supercoiled plasmid DNA by atomic force microscopy

    SciTech Connect

    Yu Jia; Zhang Zhenfeng; Cao Kou; Huang Xitai

    2008-09-26

    To study the alkali denaturation of supercoiled DNA, plasmid pBR322 was treated with gradient concentrations of NaOH solution. The results of gel electrophoresis showed that the alkali denaturation of the supercoiled DNA occurred in a narrow range of pH value (12.88-12.90). The alkali-denatured supercoiled DNA ran, as a sharp band, faster than the supercoiled DNA. The supercoiled plasmid DNA of pBR322, pACYC184 and pJGX15A were denatured by NaOH, and then visualized by atomic force microscopy. Compared with the supercoiled DNA, the atomic force microscopy images of the alkali-denatured supercoiled DNA showed rough surface with many kinks, bulges on double strands with inhomogeneous diameters. The apparent contour lengths of the denatured DNA were shortened by 16%, 16% and 50% for pBR322, pACYC184 and pJGX15A, respectively. All evidence suggested that the alkali-denatured supercoiled DNA had a stable conformation with unregistered, topologically constrained double strands and intrastrand secondary structure.

  10. 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...

  11. 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...

  12. 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...

  13. 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...

  14. 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...

  15. 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...

  16. 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...

  17. 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...

  18. Gel nanostructure in alkali-activated binders based on slag and fly ash, and effects of accelerated carbonation

    SciTech Connect

    Bernal, Susan A.; Provis, John L.; Walkley, Brant; San Nicolas, Rackel; Gehman, John D.; Brice, David G.; Kilcullen, Adam R.; Duxson, Peter; Deventer, Jannie S.J. van

    2013-11-15

    Binders formed through alkali-activation of slags and fly ashes, including ‘fly ash geopolymers’, provide appealing properties as binders for low-emissions concrete production. However, the changes in pH and pore solution chemistry induced during accelerated carbonation testing provide unrealistically low predictions of in-service carbonation resistance. The aluminosilicate gel remaining in an alkali-activated slag system after accelerated carbonation is highly polymerised, consistent with a decalcification mechanism, while fly ash-based binders mainly carbonate through precipitation of alkali salts (bicarbonates at elevated CO{sub 2} concentrations, or carbonates under natural exposure) from the pore solution, with little change in the binder gel identifiable by nuclear magnetic resonance spectroscopy. In activated fly ash/slag blends, two distinct gels (C–A–S–H and N–A–S–H) are formed; under accelerated carbonation, the N–A–S–H gel behaves comparably to fly ash-based systems, while the C–A–S–H gel is decalcified similarly to alkali-activated slag. This provides new scope for durability optimisation, and for developing appropriate testing methodologies. -- Highlights: •C-A-S-H gel in alkali-activated slag decalcifies during accelerated carbonation. •Alkali-activated fly ash gel changes much less under CO{sub 2} exposure. •Blended slag-fly ash binder contains two coexisting gel types. •These two gels respond differently to carbonation. •Understanding of carbonation mechanisms is essential in developing test methods.

  19. Effect of basic alkali-pickling conditions on the production of lysinoalanine in preserved eggs.

    PubMed

    Zhao, Yan; Luo, Xuying; Li, Jianke; Xu, Mingsheng; Tu, Yonggang

    2015-09-01

    During the pickling process, strong alkali causes significant lysinoalanine (LAL) formation in preserved eggs, which may reduce the nutritional value of the proteins and result in a potential hazard to human health. In this study, the impacts of the alkali treatment conditions on the production of LAL in preserved eggs were investigated. Preserved eggs were prepared using different times and temperatures, and alkali-pickling solutions with different types and concentrations of alkali and metal salts, and the corresponding LAL contents were measured. The results showed the following: during the pickling period of the preserved egg, the content of LAL in the egg white first rapidly increased and then slowly increased; the content of LAL in the egg yolk continued to increase significantly. During the aging period, the levels of LAL in both egg white and egg yolk slowly increased. The amounts of LAL in the preserved eggs were not significantly different at temperatures between 20 and 25ºC. At higher pickling temperatures, the LAL content in the preserved eggs increased. With the increase of alkali concentration in the alkali-pickling solution, the LAL content in the egg white and egg yolk showed an overall trend of an initial increase followed by a slight decrease. The content of LAL produced in preserved eggs treated with KOH was lower than in those treated with NaOH. NaCl and KCl produced no significant effects on the production of LAL in the preserved eggs. With increasing amounts of heavy metal salts, the LAL content in the preserved eggs first decreased and then increased. The LAL content generated in the CuSO4 group was lower than that in either the ZnSO4 or PbO groups. PMID:26188034

  20. Influence of lithium hydroxide on alkali-silica reaction

    SciTech Connect

    Bulteel, D.; Garcia-Diaz, E.; Degrugilliers, P.

    2010-04-15

    Several papers show that the use of lithium limits the development of alkali-silica reaction (ASR) in concrete. The aim of this study is to improve the understanding of lithium's role on the alteration mechanism of ASR. The approach used is a chemical method which allowed a quantitative measurement of the specific degree of reaction of ASR. The chemical concrete sub-system used, called model reactor, is composed of the main ASR reagents: reactive aggregate, portlandite and alkaline solution. Different reaction degrees are measured and compared for different alkaline solutions: NaOH, KOH and LiOH. Alteration by ASR is observed with the same reaction degrees in the presence of NaOH and KOH, accompanied by the consumption of hydroxyl concentration. On the other hand with LiOH, ASR is very limited. Reaction degree values evolve little and the hydroxyl concentration remains about stable. These observations demonstrate that lithium ions have an inhibitor role on ASR.

  1. 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.

  2. 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.

  3. Inhibitory effects of 90Sr/90Y β-irradiation on alkali burn-induced corneal neovascularization in rats

    PubMed Central

    LIN, YUANQIANG; MA, QINGJIE; LIN, SHAN; ZHOU, HONGYAN; WEN, QIANG; GAO, SHI; CHENG, GUANGHUI

    2016-01-01

    The aim of the present study was to investigate the inhibitory effects of 90Sr-90Y β-irradiation in a rat model of alkali burn-induced corneal neovascularization (CNV). Alkali burn-induced CNV was induced in the right eyes of 30 female Wistar rats, which were randomly divided into the following three groups (n=10/group): i) The alkali burn control group, which received a balanced salt solution treatment; ii) group 1, which received treatment with angiogenesis inhibitors; and iii) group 2, which received 90Sr-90Y β-irradiation treatment. A further 10 female Wistar rats comprised a blank control group and received only balanced salt solution. Digital photographs of the corneas were acquired and the area of NV was calculated. In addition, the expression levels of matrix metalloproteinase (MMP)-9, vascular endothelial growth factor (VEGF), VEGF receptor (VEGFR)-1 and VEGFR-2 in alkali-burned rat corneas were determined using western blot analysis. The results suggested that the number of new vessels and the area of CNV were significantly decreased in groups 1 and 2, as compared with the alkali burn group at each time point (P<0.05). In addition, the number of inflammatory cells and the degree of edema were decreased in groups 1 and 2, as compared with the alkali burn group, with group 2 exhibiting the most marked reduction. Western blot analysis demonstrated that the expression levels of MMP-9, VEGF, VEGFR-1 and VEGFR-2 were significantly decreased in groups 1 and 2, as compared with the alkali burn control group, with group 2 exhibiting the most significant reduction (P<0.05). The results of the present study suggested that 90Sr-90Y β-irradiation and angiogenesis inhibitor treatments were able to inhibit alkali burn-induced CNV, although 90Sr-90Y β-irradiation may be more effective. PMID:26893623

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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).

  17. 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...

  18. 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...

  19. 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...

  20. 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...

  1. 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)...

  2. 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)...

  3. 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)...

  4. 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)...

  5. 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)...

  6. 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...

  7. 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...

  8. 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...

  9. 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...

  10. 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...

  11. 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...

  12. 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...

  13. Color-Pure Violet-Light-Emitting Diodes Based on Layered Lead Halide Perovskite Nanoplates.

    PubMed

    Liang, Dong; Peng, Yuelin; Fu, Yongping; Shearer, Melinda J; Zhang, Jingjing; Zhai, Jianyuan; Zhang, Yi; Hamers, Robert J; Andrew, Trisha L; Jin, Song

    2016-07-26

    Violet electroluminescence is rare in both inorganic and organic light-emitting diodes (LEDs). Low-cost and room-temperature solution-processed lead halide perovskites with high-efficiency and color-tunable photoluminescence are promising for LEDs. Here, we report room-temperature color-pure violet LEDs based on a two-dimensional lead halide perovskite material, namely, 2-phenylethylammonium (C6H5CH2CH2NH3(+), PEA) lead bromide [(PEA)2PbBr4]. The natural quantum confinement of two-dimensional layered perovskite (PEA)2PbBr4 allows for photoluminescence of shorter wavelength (410 nm) than its three-dimensional counterpart. By converting as-deposited polycrystalline thin films to micrometer-sized (PEA)2PbBr4 nanoplates using solvent vapor annealing, we successfully integrated this layered perovskite material into LEDs and achieved efficient room-temperature violet electroluminescence at 410 nm with a narrow bandwidth. This conversion to nanoplates significantly enhanced the crystallinity and photophysical properties of the (PEA)2PbBr4 samples and the external quantum efficiency of the violet LED. The solvent vapor annealing method reported herein can be generally applied to other perovskite materials to increase their grain size and, ultimately, improve the performance of optoelectronic devices based on perovskite materials. PMID:27336850

  14. A continuously pulsed copper halide laser with a cable-capacitor Blumlein discharge circuit

    NASA Technical Reports Server (NTRS)

    Nerheim, N. M.; Bhanji, A. M.; Russell, G. R.

    1978-01-01

    Experimental characteristics of a continuously pulsed copper halide laser with a cable-capacitor Blumlein discharge circuit are reported. Quartz laser tubes 1 m in length and 1.5 and 2.5 cm in diameter were employed to study the effects of the electrical circuit, lasant, and buffer gas on laser performance. Measured properties of the Blumlein circuit are compared with an analytic solution for an idealized circuit. Both CuCl and CuBr with neon and helium buffer gas were studied. A maximum average power of 12.5 W was obtained with a 1.5 nF capacitor charged to 8 kV and discharged at 31 kHz with CuCl and neon buffer gas at 0.7 kPa in a 2.5-cm-diam tube. A maximum efficiency of 0.72 percent was obtained at 9 W average power. Measurements of the radial distribution of the power in the laser beam and the variation of laser power at 510.6 and 578.2 nm with halide vapor density are also reported. Double and continuously pulsed laser characteristics are compared, and the role of copper metastable level atoms in limiting the laser pulse energy density is discussed.

  15. Extended Photo-Conversion Spectrum in Low-Toxic Bismuth Halide Perovskite Solar Cells.

    PubMed

    Johansson, Malin B; Zhu, Huimin; Johansson, Erik M J

    2016-09-01

    Lead-based perovskites show very promising properties for use in solar cells; however, the toxicity of lead is a potential inhibitor for large-scale application of these solar cells. Here, a low-toxic bismuth halide, CsBi3I10, is synthesized from solution and the optical properties and crystal structure are compared with previously reported Cs3Bi2I9 perovskite, and the photovoltaic properties are also investigated. The XRD pattern suggests that the CsBi3I10 film has a layered structure with a different dominating crystal growth direction than the Cs3Bi2I9 perovskite. A band gap of 1.77 eV is obtained for the CsBi3I10 film, which is smaller than the band gap of Cs3Bi2I9 at 2.03 eV, and an extended visible light absorption spectrum is therefore obtained. The solar cell device with CsBi3I10 shows a photocurrent up to 700 nm, and this work shows therefore the possibility for increased light absorption and higher photocurrents in solar cells based on bismuth halide perovskites. PMID:27538852

  16. 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

  17. Nonaqueous Halide-Free Flux Reactions with Tin-Based Solders

    NASA Astrophysics Data System (ADS)

    Qu, Guoying; Weinman, Craig J.; Ghosh, Tanushree; Flake, John C.

    2015-04-01

    New halide-free fluxes are becoming more prevalent in electronic packaging; however, their efficacy and reactive behavior with conventional solders has not been well characterized. In this work, we examine nonaqueous halide-free flux reactions of tin (Sn)-based solder surfaces using electrochemical methods. Cyclic voltammetry was used to study reactions of Sn(II) and Sn(IV) species, x-ray photoelectron spectroscopy (XPS) was used to study surface chemistry, and chronopotentiometry was used to quantify equilibrium constants of Sn-carboxylic complexes. Reactions were investigated using carboxylic acid solutions such as adipic acid or maleic acid in polyethylene glycol. Carboxylic acid-based fluxes are practically inactive toward SnO2 removal at room temperature (25°C); however, some species are capable of removing the oxides at temperatures as high as 180°C and at pH as low as 0.1. XPS results suggest the H+ activity of the carboxylic acid is the key to removing SnO2 on Sn-based solder surfaces. Equilibrium coefficients and potential-pH diagrams are given to elucidate the influence of pH on Sn surfaces.

  18. Transition metal ion-assisted photochemical generation of alkyl halides and hydrocarbons from carboxylic acids

    SciTech Connect

    Carraher, Jack; Pestovsky, Oleg; Bakac, Andreja

    2012-03-14

    Near-UV photolysis of aqueous solutions of propionic acid and aqueous Fe3+ in the absence of oxygen generates a mixture of hydrocarbons (ethane, ethylene and butane), carbon dioxide, and Fe2+. The reaction becomes mildly catalytic (about five turnovers) in the presence of oxygen which converts a portion of alkyl radicals to oxidizing intermediates that reoxidize Fe2+. The photochemistry in the presence of halide ions (X− = Cl−, Br−) generates ethyl halides via halogen atom abstraction from FeXn3−n by ethyl radicals. Near-quantitative yields of C2H5X are obtained at ≥0.05 M X−. Competition experiments with Co(NH3)5Br2+ provided kinetic data for the reaction of ethyl radicals with FeCl2+ (k = (4.0 ± 0.5) × 106 M−1 s−1) and with FeBr2+ (k = (3.0 ± 0.5) × 107 M−1 s−1). Photochemical decarboxylation of propionic acid in the presence of Cu2+ generates ethylene and Cu+. Longer-chain acids also yield alpha olefins as exclusive products. These reactions become catalytic under constant purge with oxygen which plays a dual role. It reoxidizes Cu+ to Cu2+, and removes gaseous olefins to prevent accumulation of Cu+(olefin) complexes and depletion of Cu2+. The results underscore the profound effect that the choice of metal ions, the medium, and reaction conditions exert on the photochemistry of carboxylic acids.

  19. Biological neutralization of chlor-alkali industry wastewater.

    PubMed

    Jain, Rakeshkumar M; Mody, Kalpana H; Keshri, Jitendra; Jha, Bhavanath

    2011-11-01

    The present work reports biological neutralization of chlor-alkali industrial effluent by an alkaliphilic bacterium, isolated from the Gujarat coast, which was identified as Enterococcus faecium strain R-5 on the basis of morphological, biochemical and partial 16S rRNA gene sequencing. The isolate was capable of bringing down the pH of waste water from 12.0 to 7.0 within 3 h in the presence of carbon and nitrogen sources, with simultaneous reduction in total dissolved solutes (TDS) up to 19-22%. This bacterium produced carboxylic acid, as revealed by FT-IR analysis, which facilitated neutralization of alkaline effluent. The presence of unconventional raw materials viz. Madhuca indica flowers or sugar cane bagasse as carbon and nitrogen sources could effectively neutralize alkaline effluent and thus making the bioremediation process economically viable. The time required for neutralization varied with size of inoculum. To the best of our knowledge, this is the first report on biological neutralization of a chlor-alkali industrial effluent. PMID:21944194

  20. A Three Level Analytic Model for Alkali Vapor Lasers

    SciTech Connect

    Hager, Gordon D.; Perram, Glen P.

    2010-10-08

    A three level analytic model for optically pumped alkali metal vapor lasers is developed considering the steady-state rate equations for the longitudinally averaged number densities of the ground {sup 2}S{sub 1/2} and first excited {sup 2}P{sub 1/2} and {sup 2}P{sub 3/2} states. The threshold pump intensity includes both the requirements to fully bleach the pump transition and exceed optical losses, typically about 200 W/cm{sup 2}. Slope efficiency depends critically on the fraction of incident photons absorbed and the overlap of pump and resonator modes, approaching the quantum efficiency of 0.95-0.98, depending on alkali atom. For efficient operation, the collisional relaxation between the two upper levels should be fast relative to stimulated emission. By assuming a statistical distribution between the upper levels, the limiting analytic solution for the quasi-two level system is achieved. Application of the model and comparisons to recent laser demonstrations is presented.

  1. Manipulating Crystallization of Organolead Mixed-Halide Thin Films in Antisolvent Baths for Wide-Bandgap Perovskite Solar Cells.

    PubMed

    Zhou, Yuanyuan; Yang, Mengjin; Game, Onkar S; Wu, Wenwen; Kwun, Joonsuh; Strauss, Martin A; Yan, Yanfa; Huang, Jinsong; Zhu, Kai; Padture, Nitin P

    2016-01-27

    Wide-bandgap perovskite solar cells (PSCs) based on organolead (I, Br)-mixed halide perovskites (e.g., MAPbI2Br and MAPbIBr2 perovskite with bandgaps of 1.77 and 2.05 eV, respectively) are considered as promising low-cost alternatives for application in tandem or multijunction photovoltaics (PVs). Here, we demonstrate that manipulating the crystallization behavior of (I, Br)-mixed halide perovskites in antisolvent bath is critical for the formation of smooth, dense thin films of these perovskites. Since the growth of perovskite grains from a precursor solution tends to be more rapid with increasing Br content, further enhancement in the nucleation rate becomes necessary for the effective decoupling of the nucleation and the crystal-growth stages in Br-rich perovskites. This is enabled by introducing simple stirring during antisolvent-bathing, which induces enhanced advection transport of the extracted precursor-solvent into the bath environment. Consequently, wide-bandgap planar PSCs fabricated using these high quality mixed-halide perovskite thin films, Br-rich MAPbIBr2, in particular, show enhanced PV performance. PMID:26726763

  2. In vitro bioactivity investigation of alkali treated Ti6Al7Nb alloy foams

    NASA Astrophysics Data System (ADS)

    Butev, Ezgi; Esen, Ziya; Bor, Sakir

    2015-02-01

    Biocompatible Ti6Al7Nb alloy foams with 70% porosity manufactured by space holder method were activated via alkali treatment using 5 M NaOH solution at 60 °C. The interconnected pore structures enabled formation of homogenous sodium rich coating on the foam surfaces by allowing penetration of alkali solution throughout the pores which had average size of 200 μm. The resulted coating layer having 500 nm thickness exhibited porous network morphology with 100 nm pore size. On the other hand, heat treatment conducted subsequent to alkali treatment at 600 °C in air transformed sodium rich coating into crystalline bioactive sodium titanate phases. Although the coatings obtained by additional heat treatment were mechanically stable and preserved their morphology, oxidation of the samples deteriorated the compressive strength significantly without affecting the elastic modulus. However, heat treated samples revealed better hydroxyapatite formation when soaked in simulated body fluid (SBF) compared to alkali treated foams. On the other hand, untreated surfaces containing bioactive TiO2 layer were observed to comprise of Ca and P rich precipitates only rather than hydroxyapatite within 15 days. The apatite formed on the treated porous surfaces was observed to have flower-like structure with Ca/P ratio around 1.5 close to that of natural bone.

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

  4. 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

  5. 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.

  6. 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.

  7. 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

  8. 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

  9. 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 §...

  10. 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…

  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. 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

  16. Nanocrystals of Cesium Lead Halide Perovskites (CsPbX3, X = Cl, Br, and I): Novel Optoelectronic Materials Showing Bright Emission with Wide Color Gamut

    PubMed Central

    2015-01-01

    Metal halides perovskites, such as hybrid organic–inorganic CH3NH3PbI3, are newcomer optoelectronic materials that have attracted enormous attention as solution-deposited absorbing layers in solar cells with power conversion efficiencies reaching 20%. Herein we demonstrate a new avenue for halide perovskites by designing highly luminescent perovskite-based colloidal quantum dot materials. We have synthesized monodisperse colloidal nanocubes (4–15 nm edge lengths) of fully inorganic cesium lead halide perovskites (CsPbX3, X = Cl, Br, and I or mixed halide systems Cl/Br and Br/I) using inexpensive commercial precursors. Through compositional modulations and quantum size-effects, the bandgap energies and emission spectra are readily tunable over the entire visible spectral region of 410–700 nm. The photoluminescence of CsPbX3 nanocrystals is characterized by narrow emission line-widths of 12–42 nm, wide color gamut covering up to 140% of the NTSC color standard, high quantum yields of up to 90%, and radiative lifetimes in the range of 1–29 ns. The compelling combination of enhanced optical properties and chemical robustness makes CsPbX3 nanocrystals appealing for optoelectronic applications, particularly for blue and green spectral regions (410–530 nm), where typical metal chalcogenide-based quantum dots suffer from photodegradation. PMID:25633588

  17. Synthesis and structure of the ternary and quaternary strontium nitride halides, Sr{sub 2}N(X, X') (X, X'=Cl, Br, I)

    SciTech Connect

    Bowman, Amy; Smith, Ronald I.; Gregory, Duncan H. . E-mail: Duncan.Gregory@Nottingham.ac.uk

    2006-01-15

    A number of new, layered nitride mixed halides have been synthesised in the quaternary phase systems Sr-N-Cl-Br and Sr-N-Br-I. The variation in structure with composition has been investigated by powder X-ray and powder neutron diffraction techniques and the structure of strontium nitride iodide, Sr{sub 2}NI, has been determined for the first time (rhombohedral space group R-3m, a=4.0103(1)A, c=23.1138(2)A, Z=3). A continuous solid solution exists between Sr{sub 2}NCl and Sr{sub 2}NBr with intermediate compounds adopting the same anti-{alpha}-NaFeO{sub 2} structure (rhombohedral space group R-3m) as the ternary end members. A similar smooth and linear relationship between structure and composition is seen from Sr{sub 2}NBr to Sr{sub 2}NI and hence cubic close packing of metal-nitrogen layers is adopted regardless of halide, X (X'). While nitride and halide anions occupy distinct crystallographic sites, there is no ordering of the halides in the quaternary materials irrespective of stoichiometry or temperature (between 3 and 673K)

  18. Ternary and quaternary layered nitride halides, Ca{sub 2}N(X,X') (X,X'=Cl, Br, I): Evolution of structure with composition

    SciTech Connect

    Bowman, Amy; Smith, Ronald I.; Gregory, Duncan H. . E-mail: Duncan.Gregory@Nottingham.ac.uk

    2005-06-15

    The quaternary systems Ca-N-Cl-Br and Ca-N-Br-I have been investigated resulting in the synthesis of a number of new layered nitride mixed halides. The evolution of structure with composition has been investigated by powder X-ray and powder neutron diffraction techniques. A continuous solid solution exists between Ca{sub 2}NCl and Ca{sub 2}NBr with intermediate compounds adopting the same anti- {alpha}-NaFeO{sub 2} structure (rhombohedral space group R3-bar m) as the ternary end members. A phase transition occurs in the Ca{sub 2}NBr{sub 1-y}I{sub y} system between y=0.7 and y=0.8 corresponding to a switch from cubic close packing to hexagonal close packing of metal-nitrogen layers and corresponding adoption of the anti-{beta}-RbScO{sub 2} (filled anti-CdI{sub 2}) structure (hexagonal space group P6{sub 3}/mmc). While nitride and halide anions occupy distinct crystallographic sites, there is no ordering of halides in quaternary materials irrespective of stoichiometry or structure type. All the nitride halides show temperature independent paramagnetic behaviour between 2 and 300K.

  19. 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

  20. 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

  1. Thermodynamic Origin of Photoinstability in the CH3NH3Pb(I1-xBrx)3 Hybrid Halide Perovskite Alloy.

    PubMed

    Brivio, Federico; Caetano, Clovis; Walsh, Aron

    2016-03-17

    The formation of solid-solutions of iodide, bromide, and chloride provides the means to control the structure, band gap, and stability of hybrid halide perovskite semiconductors for photovoltaic applications. We report a computational investigation of the CH3NH3PbI3/CH3NH3PbBr3 alloy from density functional theory with a thermodynamic analysis performed within the generalized quasi-chemical approximation. We construct the phase diagram and identify a large miscibility gap, with a critical temperature of 343 K. The observed photoinstability in some mixed-halide solar cells is explained by the thermodynamics of alloy formation, where an initially homogeneous solution is subject to spinodal decomposition with I and Br-rich phases, which is further complicated by a wide metastable region defined by the binodal line. PMID:26952337

  2. Proposal for halogen atom transfer mechanism for Ullmann O-arylation of phenols with aryl halides.

    PubMed

    Zhang, Songlin; Zhu, Zhenzhong; Ding, Yuqiang

    2012-12-01

    A systematic theoretical study on reaction mechanisms for copper(I)-catalyzed C-O coupling of phenols with aryl bromides is reported herein. Through evaluation of the relative concentrations of possible copper species in reaction solution and reactivity study of these copper species with aryl halides in the context of several commonly proposed mechanisms for copper(I)-catalyzed Ullmann reactions, we propose that the active copper catalyst should be a neutral (L)Cu(I)-OAr (L denotes an ancillary ligand; OAr denotes an aryloxide ligand) species in nonpolar solvent and Cu(OAr)(2)(-) anion in highly polar solvent. In the reaction solution, these two kinds of copper species should be in equilibrium, the direction of which is highly dependent on the polarity of the solvent. For both kinds of copper species, a halogen atom transfer mechanism is favored where an initial halogen atom transfer from phenyl bromide to the Cu(I) center occurs, resulting in the formation of Cu(II)(OAr)(Br) and a phenyl radical. Subsequent rapid attack of this phenyl radical to the aryloxide ligand bound to copper(II) would yield the coupling product and Cu(I)(Br) species, which can be readily converted to the active Cu(I)-OAr species in the presence of phenols and base. Other mechanisms such as oxidative addition, single electron transfer and σ-bond metathesis mechanisms all possess activation barriers which are too high, rendering them kinetically unfavorable. Electronic effects on phenol rings reveal that electron-donating substituents accelerate the coupling of (phen)Cu(I)(OAr) with aryl halides whereas electron-withdrawing substituents lead to much higher activation barriers, which is consistent with experimental findings and thus lends further support for such a halogen atom transfer mechanism. In view of the widely accepted oxidative addition/reductive elimination mechanism for analogous copper(I)-catalyzed coupling of N-nucleophiles with aryl halides, our results here highlight that the

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. Process for treating spent catalyst including antimony halides from chlorofluorocarbon production

    SciTech Connect

    Kalcevic, V.; McGahan, J.F.

    1988-06-14

    A process for treating spent catalyst from chlorofluorocarbon production is described wherein the catalyst includes antimony halides and undergoes hydrolysis in an aqueous medium to produce insoluble antimony compounds and fluoride ions. The process comprises hydrolyzing the catalyst in an aqueous solution of ferric chloride having a sufficient concentration of ferric ions to complex substantially all of the fluoride ions produced upon hydrolysis of the catalyst, neutralizing the reaction mass present following hydrolysis of the catalyst and complexing of the fluoride ions by contacting the reaction mass with an aqueous suspension of a compound selected from the class consisting of calcium hydroxide and magnesium hydroxide, and separating the insoluble antimony compounds from the neutralized reaction mass.

  9. Self-regulation mechanism for charged point defects in hybrid halide perovskites

    SciTech Connect

    Walsh, Aron; Scanlon, David O.; Chen, Shiyou; Gong, X. G.; Wei, Su -Huai

    2014-12-11

    Hybrid halide perovskites such as methylammonium lead iodide (CH3NH3PbI3) exhibit unusually low free-carrier concentrations despite being processed at low-temperatures from solution. We demonstrate, through quantum mechanical calculations, that an origin of this phenomenon is a prevalence of ionic over electronic disorder in stoichiometric materials. Schottky defect formation provides a mechanism to self-regulate the concentration of charge carriers through ionic compensation of charged point defects. The equilibrium charged vacancy concentration is predicted to exceed 0.4 % at room temperature. Furthermore, this behavior, which goes against established defect conventions for inorganic semiconductors, has implications for photovoltaic performance.

  10. Mechanical and microstructural properties of alkali-activated fly ash geopolymers.

    PubMed

    Komljenović, M; Bascarević, Z; Bradić, V

    2010-09-15

    This paper investigates the properties of geopolymer obtained by alkali-activation of fly ash (FA), i.e. the influence of characteristics of the representative group of FA (class F) from Serbia, as well as that of the nature and concentration of various activators on mechanical and microstructural properties of geopolymers. Aqueous solutions of Ca(OH)(2), NaOH, NaOH+Na(2)CO(3), KOH and sodium silicate (water glass) of various concentrations were used as alkali activators. It was established that the nature and concentration of the activator was the most dominant parameter in the alkali-activation process. In respect of physical characteristics of FA, the key parameter was fineness. The geopolymer based on FA with the highest content of fine particles (<43 microm), showed the highest compressive strength in all cases. Regardless of FA characteristics, nature and concentration of the activator, the alkali-activation products were mainly amorphous. The formation of crystalline phases (zeolites) occurred in some cases, depending on the reaction conditions. The highest compressive strength was obtained using sodium silicate. Together with the increase of sodium silicate SiO(2)/Na(2)O mass ratio, the atomic Si/Al ratio in the reaction products was also increased. Under the experimental conditions of this investigation, high strength was directly related to the high Si/Al ratio. PMID:20554110

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. Transport properties of alkali metal doped fullerides

    SciTech Connect

    Yadav, Daluram Yadav, Nishchhal

    2015-07-31

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

  17. Transport properties of alkali metal doped fullerides

    NASA Astrophysics Data System (ADS)

    Yadav, Daluram; Yadav, Nishchhal

    2015-07-01

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

  18. 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

  19. 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

  20. Concentration Effects and Ion Properties Controlling the Fractionation of Halides during Aerosol Formation

    NASA Technical Reports Server (NTRS)

    Guzman, Marcelo I.; Athalye, Richa R.; Rodriguez, Jose M.

    2012-01-01

    During the aerosolization process at the sea surface, halides are incorporated into aerosol droplets, where they may play an important role in tropospheric ozone chemistry. Although this process may significantly contribute to the formation of reactive gas phase molecular halogens, little is known about the environmental factors that control how halides selectively accumulate at the air-water interface. In this study, the production of sea spray aerosol is simulated using electrospray ionization (ESI) of 100 nM equimolar solutions of NaCl, NaBr, NaI, NaNO2, NaNO3, NaClO4, and NaIO4. The microdroplets generated are analyzed by mass spectrometry to study the comparative enrichment of anions (f (Isub x-)) and their correlation with ion properties. Although no correlation exists between f (sub x-) and the limiting equivalent ionic conductivity, the correlation coefficient of the linear fit with the size of the anions R(sub x-), dehydration free-energy ?Gdehyd, and polarizability alpha, follows the order: (R(sub x-)(exp -2)) > (R(sub x-)(exp -1)) >(R(sub x-) > delta G(sub dehyd) > alpha. The same pure physical process is observed in H2O and D2O. The factor f (sub x-) does not change with pH (6.8-8.6), counterion (Li+, Na+, K+, and Cs+) substitution effects, or solvent polarity changes in methanol - and ethanol-water mixtures (0 <= xH2O <= 1). Sodium polysorbate 20 surfactant is used to modify the structure of the interface. Despite the observed enrichment of I- on the air-water interface of equimolar solutions, our results of seawater mimic samples agree with a model in which the interfacial composition is increasingly enriched in I- < Br- < Cl- over the oceanic boundary layer due to concentration effects in sea spray aerosol formation.