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At least 37 records · Page 2

Electrodeposition of Metals in Microgravity Conditions

Metal electrodeposition may introduce various morphological variations depending on the electrolytic conditions including cell configurations. For liquid electrolytes, a precise study of these deposits may be complicated by convective motion due to buoyancy. Zero-gravity (0-G) condition provided by drop shaft or parabolic flight gives a straightforward mean to avoid this effect: we present here 0-G electrodeposition experiments, which we compare to ground experiments (1-G). Two electrochemical systems were studied by laser interferometry, allowing to measure the concentration variations in the electrolyte: copper deposition from copper sulfate aqueous solution and lithium deposition from an ionic liquid containing LiTFSI. For copper, concentration variations were in good agreement with theory. For lithium, an apparent induction time was observed for the concentration evolution at 1-G: due to this induction time and to the low diffusion coefficient in ionic liquid, the concentration variations were hardly measurable in the parabolic flight 0-G periods of 20 seconds.

Nishikawa, K.↗

Computational and Experimental Investigation of Li-doped Ionic Liquid Electrolytes: [pyr14][tfsi], [pyr13][fsi], and [EMIM][BF4]

We employ molecular dynamics (MD) simulation and experiment to investigate the structure, thermodynamics, and transport of N-methyl-N-butylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N -methyl-N-propylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li-salt mole fraction (0.05 xLi+ 0.33) and temperature (298 K T 393 K). Structurally, Li+ is shown to be solvated by three anion neigh- bors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of xLi+ we find the presence of lithium aggregates. Pulsed field gradient spin-echo NMR measurements of diffusion and electrochemical impedance spectroscopy measurements of ionic conductivity are made for the neat ionic liquids as well as 0.5 molal solutions of Li-salt in the ionic liquids. Bulk ionic liquid properties (density, diffusion, viscosity, and ionic conductivity) are obtained with MD and show excellent agreement with experiment. While the diffusion exhibits a systematic decrease with increasing xLi+, the contribution of Li+ to ionic conductivity increases until reach- ing a saturation doping level of xLi+ 0.10. Comparatively, the Li+ conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1-0.3 mScm. Our transport results also demonstrate the necessity of long MD simulation runs ( 200 ns) required to converge transport properties at room T. The differences in Li+ transport are reflected in the residence times of Li+ with the anions (Li), which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, to comment on the relative kinetics of Li+ transport in each liquid, we find that while the net motion of Li+ with its solvation shell (vehicular) significantly contributes to net diffusion in all liquids, the importance of transport through anion exchange (hopping) increases at high xLi+ and in liquids with large anions.

electrolytes↗

Kinetic Monte Carlo Investigation of the Effects of Vacancy Pairing on Oxygen Diffusivity in Yttria-Stabilized Zirconia

Yttria-stabilized zirconia s high oxygen diffusivity and corresponding high ionic conductivity, and its structural stability over a broad range of temperatures, have made the material of interest for use in a number of applications, for example, as solid electrolytes in fuel cells. At low concentrations, the stabilizing yttria also serves to increase the oxygen diffusivity through the presence of corresponding oxygen vacancies, needed to maintain charge neutrality. At higher yttria concentration, however, diffusivity is impeded by the larger number of relatively high energy migration barriers associated with yttrium cations. In addition, there is evidence that oxygen vacancies preferentially occupy nearest-neighbor sites around either dopant or Zr cations, further affecting vacancy diffusion. We present the results of ab initio calculations that indicate that it is energetically favorable for oxygen vacancies to occupy nearest-neighbor sites adjacent to Y ions, and that the presence of vacancies near either species of cation lowers the migration barriers. Kinetic Monte Carlo results from simulations incorporating this effect are presented and compared with results from simulations in which the effect is not present.

Good, Brian S.↗

Metallization for Yb14MnSb11-Based Thermoelectric Materials

Thermoelectric materials provide a means for converting heat into electrical power using a fully solid-state device. Power-generating devices (which include individual couples as well as multicouple modules) require the use of ntype and p-type thermoelectric materials, typically comprising highly doped narrow band-gap semiconductors which are connected to a heat collector and electrodes. To achieve greater device efficiency and greater specific power will require using new thermoelectric materials, in more complex combinations. One such material is the p-type compound semiconductor Yb14MnSb11 (YMS), which has been demonstrated to have one of the highest ZT values at 1,000 C, the desired operational temperature of many space-based radioisotope thermoelectric generators (RTGs). Despite the favorable attributes of the bulk YMS material, it must ultimately be incorporated into a power-generating device using a suitable joining technology. Typically, processes such as diffusion bonding and/or brazing are used to join thermoelectric materials to the heat collector and electrodes, with the goal of providing a stable, ohmic contact with high thermal conductivity at the required operating temperature. Since YMS is an inorganic compound featuring chemical bonds with a mixture of covalent and ionic character, simple metallurgical diffusion bonding is difficult to implement. Furthermore, the Sb within YMS readily reacts with most metals to form antimonide compounds with a wide range of stoichiometries. Although choosing metals that react to form high-melting-point antimonides could be employed to form a stable reaction bond, it is difficult to limit the reactivity of Sb in YMS such that the electrode is not completely consumed at an operating temperature of 1,000 C. Previous attempts to form suitable metallization layers resulted in poor bonding, complete consumption of the metallization layer or fracture within the YMS thermoelement (or leg).

Firdosy, Samad↗

Variability of intensity ratios of H to He and He to ions with Z not smaller than 3 in solar energetic particle events

Data from the solid-state detector on Explorer 35 are applied to a study of two intensity ratios in the sub-MeV per nucleon specific kinetic energy range for several energetic particle events. It is found that the intensity ratios vary markedly from event to event, particularly during the time history of the individual events. This implies that the ratios have no simple relationship to 'solar abundances' in the usual sense of the term. The pattern of the variability of each ratio is established; the ratio of He to ions with Z not smaller than 3 starts with a low value and increases as the event proceeds. The H/He ratio exhibits a qualitatively similar time history with marked relative enhancement of He early in an event. Differential diffusion of the various ionic species with differing magnetic rigidities is seen to be the dominant physical cause for the variabilities observed.

Van Allen, J. A.↗

Inexpensive cross-linked polymeric separators made from water soluble polymers

Polyvinyl alcohol (PVA) crosslinked chemically with aldehyde reagents produces membranes which demonstrate oxidation resistance, dimensional stability, low ionic resistivity, low zincate diffusivity, and low zinc dendrite penetration rate which make them suitable for use as alkaline battery separators. They are intrinsically low in cost and environmental health and safety problems associated with commercial production appear minimal. Preparation, property measurements, and cell test results in Ni/Zn and Ag/Zn cells are described and discussed.

Hsu, L. C.↗

The gabbro-eclogite phase transition and the elevation of mountain belts on Venus

The hypothesis is explored that the crust-mantle boundary of Venus is not in phase equilibrium but rather is rate-limited by the temperature-dependent volume diffusion of the slowest ionic species. The 1D thermal evolution problem is solved assuming that the mountains formed by uniform horizontal shortening of the crust and the lithospheric mantle at a constant rate. The time-dependent density structure and surface elevation are calculated by assuming a temperature-dependent reaction rate and local Airy isostatic compensation. For a horizontal strain rate of 10 exp -15/s or greater, the temperature increase at the base of the crust during mountain formation is modest to negligible, the deepening lower crust is metastable, and the surface elevation increases as the crust thickens. For strain rates less than 10 exp -16/s, crustal temperature increases with time because of internal heat production and the lower crust is more readily transformed to the dense eclogite assemblage. For such models, a maximum elevation is reached during crustal shortening.

Namiki, Noriyuki↗

Permeation of halide anions through phospholipid bilayers occurs by the solubility-diffusion mechanism

Two alternative mechanisms are frequently used to describe ionic permeation of lipid bilayers. In the first, ions partition into the hydrophobic phase and then diffuse across (the solubility-diffusion mechanism). The second mechanism assumes that ions traverse the bilayer through transient hydrophilic defects caused by thermal fluctuations (the pore mechanism). The theoretical predictions made by both models were tested for halide anions by measuring the permeability coefficients for chloride, bromide, and iodide as a function of bilayer thickness, ionic radius, and sign of charge. To vary the bilayer thickness systematically, liposomes were prepared from monounsaturated phosphatidylcholines (PC) with chain lengths between 16 and 24 carbon atoms. The fluorescent dye MQAE (N-(ethoxycarbonylmethyl)-6-methoxyquinolinium bromide) served as an indicator for halide concentration inside the liposomes and was used to follow the kinetics of halide flux across the bilayer membranes. The observed permeability coefficients ranged from 10(-9) to 10(-7) cm/s and increased as the bilayer thickness was reduced. Bromide was found to permeate approximately six times faster than chloride through bilayers of identical thickness, and iodide permeated three to four times faster than bromide. The dependence of the halide permeability coefficients on bilayer thickness and on ionic size were consistent with permeation of hydrated ions by a solubility-diffusion mechanism rather than through transient pores. Halide permeation therefore differs from that of a monovalent cation such as potassium, which has been accounted for by a combination of the two mechanisms depending on bilayer thickness.

NASA Discipline Exobiology↗

Ion morphology in the inner tail of Comet P/Halley

Comet Halley CCD images taken in the light of CO(+) and H2O(+) were analyzed. Most of the ionic emission originates in a diffuse component on which the ion ray structure appears to be superimposed. On average, the peak enhancement in the CO(+) rays is 20% over the adjacent minima, where the emission is due to the underlying component. The H2O(+):CO(+) ratio varies by as much as 30% from ray to ray.

Hoban, Susan↗

Ground-based observations of comets, the Jupiter plasma Torus, and Io

Aspects of cometary and magnetospheric physics were investigated by means of ground-based astronomical spectroscopy. High-throughput, dual-etalon Fabry-Perot spectrometers were used to obtain very high resolution spectra of atomic, molecular, and ionic emission lines from the diffuse gases and plasmas associated with comets and the Jupiter plasma torus. The Fabry-Perot spectrometers were also used with a charge coupled device (CCD) camera to obtain images of these extended emission sources in individual spectral lines at high spectral resolution. A new program using the McMath solar-stellar spectrograph to observe emission lines from Io was recently initiated. The McMath spectrograph has a high resolution mode which allows the detection of narrow, relatively faint emission lines superimposed on Io's reflected solar spectrum.

Scherb, Frank↗

Fundamental Aspects of Ion Transport in Solid Electrolytes

Solid electrolytes (also termed as superionic solids or fast ion conductors) are characterized by high electrical conductivity, comparable to concentrated liquid electrolytes or even molten salt electrolytes, made possible by rapid transport of ions in the crystalline lattice.

electrochemistry solid state ionics superionic sol↗

Solute diffusion in liquid metals

A gas model of diffusion in liquid metals is presented. In this model, ions of liquid metals are assumed to behave like the molecules in a dense gas. Diffusion coefficient of solute is discussed with reference to its mass, ionic size, and pair potential. The model is applied to the case of solute diffusion in liquid silver. An attempt was made to predict diffusion coefficients of solutes with reasonable accuracy.

Bhat, B. N.↗

Effect of microstructure on Na/+/ diffusion in beta alumina

The effect of microstructural features, such as grain size and orientation, on sodium ion diffusion in polycrystalline beta alumina is investigated; the ionic solid is suitable for use in high-energy and power density batteries. Two types of hot-pressed polycrystalline samples are studied, one with grains highly oriented in the direction normal to the pressing direction, the other with significantly less preferred orientation normal to the pressing direction. Results of the experimental assessments indicate that grain size and diffusion path tortuosity have little effect on diffusion kinetics, while grain boundary type and grain aspect ratio are important factors in determining the diffusion rate.

Sarian, S.↗

Thermal diffuse X-ray scattering in simple metals

Calculations are reported for the ionic structure factor and X-ray scattering cross section of sodium (at T=0 K and 90 K) and lithium (both isotopes at T=0 K) within the harmonic approximation. An evaluation of the appropriate displacement- displacement correlation function by the special point method circumvents the need for a multiphonon expansion. In the case of sodium, the structure in the one-phonon scattering was straightforwardly accounted for, and an approximate expansion was obtained for all multiphonon scattering. By treating core and conduction electrons on an equal footing, it is shown that information on the conduction electron system is present in the forward scattering component. In lithium the one-phonon cross section at small angles aids in the determination of the effective electron-ion interaction.

Straus, D. M.↗

Termolecular ionic recombination at high ambient gas density

It is shown that the importance of diffusion relative to drift in ion-ion recombination is a decreasing function of the separation between the ions (contrary to a common supposition). Langevin's formula for the recombination coefficient is obtained very simply using a physical model which allows for both diffusion and drift.

Bates, D. R.↗

Inexpensive cross-linked polymeric separators made from water-soluble polymers

Polyvinyl alcohol (PVA), cross-linked chemically with aldehyde reagents, produces membranes which demonstrate oxidation resistance, dimensional stability, low ionic resistivity (less than 0.8 Ohms sq cm), low zincate diffusivity (less than 1 x 10 to the -7th mols/sq cm per min), and low zinc dendrite penetration rate (greater than 350 min) which make them suitable for use as alkaline battery separators. They are intrinsically low in cost, and environmental health and safety problems associated with commercial production appear minimal. Preparation, property measurements, and cell test results in Ni/Zn and Ag/Zn cells are described and discussed.

Hsu, L.-C.↗