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At least 19 records

Silicon oxidation in fluoride solutions

Silicon is produced in a NaF, Na2SiF6, and Na matrix when SiF4 is reduced by metallic sodium. Hydrogen is evolved during acid leaching to separate the silicon from the accompanying reaction products, NaF and Na2SiF6. The hydrogen evolution reaction was studied under conditions simulating leaching conditions by making suspensions of the dry silicon powder in aqueous fluoride solutions. The mechanism for the hydrogen evolution is discussed in terms of spontaneous oxidation of silicon resulting from the cooperative effects of (1) elemental sodium in the silicon that reacts with water to remove a protective silica layer, leaving clean reactive silicon, and (2) fluoride in solution that complexes with the oxidized silicon in solution and retards formation of a protective hydrous oxide gel.

Sancier, K. M.

AC impedance study of degradation of porous nickel battery electrodes

AC impedance spectra of porous nickel battery electrodes were recorded periodically during charge/discharge cycling in concentrated KOH solution at various temperatures. A transmission line model (TLM) was adopted to represent the impedance of the porous electrodes, and various model parameters were adjusted in a curve fitting routine to reproduce the experimental impedances. Degradation processes were deduced from changes in model parameters with electrode cycling time. In developing the TLM, impedance spectra of planar (nonporous) electrodes were used to represent the pore wall and backing plate interfacial impedances. These data were measured over a range of potentials and temperatures, and an equivalent circuit model was adopted to represent the planar electrode data. Cyclic voltammetry was used to study the characteristics of the oxygen evolution reaction on planar nickel electrodes during charging, since oxygen evolution can affect battery electrode charging efficiency and ultimately electrode cycle life if the overpotential for oxygen evolution is sufficiently low.

Lenhart, Stephen J.

The application of electrochemical impedance spectroscopy for characterizing the degradation of Ni(OH)2/NiOOH electrodes

Electrochemical impedance spectra of rolled and bonded and sintered porous nickel battery electrodes were recorded periodically during charge/discharge cycling in concentrated KOH solution at various temperatures. A transmission line model (TLM) was adopted to represent the impedance of the porous electrodes, and various model parameters were adjusted in a curve fitting routine to reproduce the experimental impedances. Degradation processes for rolled and bonded electrodes were deduced from changes in model parameters with electrode cycling time. In developing the TLM, impedance spectra of planar (non-porous) electrodes were used to represent the pore wall and backing plate interfacial impedances. These data were measured over a range of potentials and temperatures, and an equivalent circuit model was adopted to represent the planar electrode data. Cyclic voltammetry was used to study the characteristics of the oxygen evolution reaction on planar nickel electrodes during charging, since oxygen evolution can affect battery electrode charging efficiency and ultimately electrode cycle life if the overpotential for oxygen evolution is sufficiently low. Transmission line modeling results suggest that porous rolled and bonded nickel electrodes undergo restructuring during charge/discharge cycling prior to failure.

Macdonald, D. D.

The possible role of solid surface area in condensation reactions during chemical evolution - Reevaluation

Using surface concentration and reaction rate as the main criteria for the feasibility of condensation reactions, four types of prebiotic environments were analyzed: (1) an ocean-sediment system, (2) a dehydrated lagoon bed produced by evaporation, (3) the surface of a frozen sediment, and (4) a fluctuating system where hydration (rainstorms, tidal variations, flooding) and dehydration (evaporation) take place in a cyclic manner. With the possible exception of nucleotides, low adsorption of organomonomers on sediment surfaces of a prebiotic ocean (pH 8) is expected, and significant condensation is considered unlikely. In dehydrated and frozen systems, high surface concentrations are probable and condensation is more likely. In fluctuating environments, condensation rates will be enhanced and the size distribution of the oligomers formed during dehydration may be influenced by a 'redistribution mechanism' in which adsorbed oligomers and monomers are desorbed and redistributed on the solid surface during the next hydration-dehydration cycle.

Lahav, N.

Evolution of a reaction center in an explosive material

Consideration is given to the spatial structure and temporal evolution of a reaction center for a model involving Arrhenius kinetics. The center, which is characterized by peaks in pressure and temperature with little diminution in local density, is found to have one of two possible self-similar structures. The analysis uses a combination of asymptotics and numerics and terminates when pressure and temperature in the reaction center have peaked.

Jackson, T. L.

Requirements for optimization of electrodes and electrolyte for the iron/chromium Redox flow cell

Improved catalyzation techniques that included a pretreatment of carbon substrate and provided normalized carbon surface for uniform gold deposition were developed. This permits efficient use of different batches of carbon felt materials which initially vary significantly in their physical and surface chemical properties, as well as their electrochemical behavior. Further modification of gold impregnation technique gave the best performing electrodes. In addition to the linear sweep voltammetry, cyclic voltammetry was used to determine the effects of different activation procedures on the Cr(3)/Cr(2) Redox and H2 evolution reactions. The roles of carbon, gold and lead in the overall Redox cycle are identified. The behavior of the electrodes at both normal battery operating potentials and more extreme potentials is discussed preparing efficient and stable electrodes for the energy storage battery is implicated.

Jalan, V.

An electrochemical study of the corrosion behavior of primer coated 2219-T87 aluminum

The corrosion behavior for 2219-T87 aluminum coated with various primers, including those used for the external tank and solid rocket boosters of the Space Shuttle Transportation System, were investigated using electrochemical techniques. Corrosion potential time, polarization resistance time, electrical resistance time, and corrosion rate time measurements were all investigated. It was found that electrical resistance time and corrosion rate time measurement were most useful for studying the corrosion behavior of painted aluminum. Electrical resistance time determination give useful information concerning the porosity of paint films, while corrosion rate time curves give important information concerning overall corrosion rates and corrosion mechanisms. In general, the corrosion rate time curves all exhibited at least one peak during the 30 day test period, which was attributed, according to the proposed mechanisms, to the onset of the hydrogen evolution reaction and the beginning of destruction of the protective properties of the paint film.

Danford, M. D.

Assessing corrosion problems in photovoltaic cells via electrochemical stress testing

A series of accelerated electrochemical experiments to study the degradation properties of polyvinylbutyral-encapsulated silicon solar cells has been carried out. The cells' electrical performance with silk screen-silver and nickel-solder contacts was evaluated. The degradation mechanism was shown to be electrochemical corrosion of the cell contacts; metallization elements migrate into the encapsulating material, which acts as an ionic conducting medium. The corrosion products form a conductive path which results in a gradual loss of the insulation characteristics of the encapsulant. The precipitation of corrosion products in the encapsulant also contributes to its discoloration which in turn leads to a reduction in its transparency and the consequent optical loss. Delamination of the encapsulating layers could be attributed to electrochemical gas evolution reactions. The usefulness of the testing technique in qualitatively establishing a reliability difference between metallizations and antireflection coating types is demonstrated.

Shalaby, H.

Characterization of the relationship of the cure cycle chemistry to cure cycle processing properties

Dynamic Dielectric measurements made over a wide range of frequency provide a sensitive and convenient means for monitoring the cure process in thermosets and thermoplastics. The measurement of dielectric relaxation is one of only a few instrumental techniques available for studying molecular properties in both the liquid and solid states. Furthermore, it is probably the only convenient experimental technique for studying the polymerization process of going from a monomeric liquid of varying viscosity to a crosslinked, insoluble, high temperature solid. The objective of the research is to develop on-line dielectric instrumentation for quantitative nondestructive material evaluation and closed loop smart cure cycle control. The key is to relate the chemistry of the cure cycle process to the dielectric properties of the polymer system by correlating the time, temperature, and frequency dependent dielectric measurements with chemical characterization measurements. Measurement of the wide variation in magnitude of the complex permittivity with both frequency and state of cure, coupled with chemical characterization work, have been shown in the laboratory to have the potential to determine: resin quality, composition and age; cure cycle window boundaries; onset of flow and point of maximum flow; extent of and completion of reaction; evolution of volatiles; T sub g; and, crosslinking and molecular weight buildup.

Kranbuehl, D. E.

Hydrogen embrittlement in nickel-hydrogen cells

It was long known that many strong metals can become weakened and brittle as the result of the accumulation of hydrogen within the metal. When the metal is stretched, it does not show normal ductile properties, but fractures prematurely. This problem can occur as the result of a hydrogen evolution reaction such as corrosion or electroplating, or due to hydrogen in the environment at the metal surface. High strength alloys such as steels are especially susceptible to hydrogen embrittlement. Nickel-hydrogen cells commonly use Inconel 718 alloy for the pressure container, and this also is susceptible to hydrogen embrittlement. Metals differ in their susceptibility to embrittlement. Hydrogen embrittlement in nickel-hydrogen cells is analyzed and the reasons why it may or may not occur are discussed. Although Inconel 718 can display hydrogen embrittlement, experience has not identified any problem with nickel-hydrogen cells. No hydrogen embrittlement problem is expected with the 718 alloy pressure container used in nickel-hydrogen cells.

Gross, Sidney

Spectroscopy and reactions of molecules important in chemical evolution

The research includes: (1) hot hydrogen atom reactions in terms of the nature of products produced, mechanism of the reactions and the implication and application of such reactions for molecules existing in interstellar clouds, in planetary atmospheres, and in chemical evolution; (2) photochemical reactions that can lead to molecules important in chemical evolution, interstellar clouds and as constituents in planetary atmospheres; and (3) spectroscopic and theoretical properties of biomolecules and their precursors and where possible, use these to understand their photochemical behavior.

Becker, R. S.

Design evolution of the orbiter reaction control subsystem

The challenges of space shuttle orbiter reaction control subsystem development began with selection of the propellant for the subsystem. Various concepts were evaluated before the current Earth storable, bipropellant combination was selected. Once that task was accomplished, additional challenges of designing the system to satisfy the wide range of requirements dictated by operating environments, reusability, and long life were met. Verification of system adequacy was achieved by means of a combination of analysis and test. The studies, the design efforts, and the test and analysis techniques employed in meeting the challenges are described.

Taeber, R. J.

Hot hydrogen atoms reactions of interest in molecular evolution and interstellar chemistry

Hot hydrogen atoms which are photochemically generated initiate reactions among mixtures of methane, ethane, water and ammonia, to produce ethanol, organic amines, organic acids, and amino acids. Both ethanol and ethyl amine can also act as substrates for formation of amino acids. The one carbon substrate methane is sufficient as a carbon source to produce amino acids. Typical quantum yields for formation of amino acids are approximately 0.00002 to 0.00004. In one experiment, 6 protein amino acids were identified and 8 nonprotein amino acids verified utilizing gas chromatography-mass spectroscopy. We propose that hot atoms, especially hydrogen, initiate reactions in the thermodynamic nonequilibrium environment of interstellar space as well as in the atmospheres of planets.

Becker, R. S.

The evolution of nitrogen cycling

The energetics of nitrogen transformation reactions and the evolution of nitrogen cycling are examined. It is suggested that meteor impact-produced fixed nitrogen could have caused the entire reservoir of the earth's N2 to convert into fixed nitrogen at the end of accretion. The abiotic fixation rate on the early earth by lightning is estimated at about 1-3 X 10 to the 16th molecules of NO/J. It is found that biological nitrogen fixation may have evolved after the development of an aerobic atmosphere. It is shown that HNO could eventually become NO2(-) and NO3(-) after reaching the earth's surface. It is concluded that the evolutionary sequence for the biological transformation of nitrogen compounds is ammonification - denitrification - nitrification - nitrogen fixation.

Mancinelli, Rocco L.

Hot hydrogen atoms - Initiators of reactions of interest in interstellar chemistry and evolution

Hot hydrogen atoms possess kinetic (or translational) energy in excess of that to be expected if the atoms were in thermal equilibrium with the surroundings. In the investigation reported the hot hydrogen atoms were generated by the photolysis of donor molecules. The light sources for the photolysis were 1000-watt xenon or 500-watt mercury lamps combined with a filter system. The experiments show that hot hydrogen atoms can initiate reactions among simple molecules to produce biomolecules of significance.

Hong, K.-Y.

Chemical evolution. XL - Clay-mediated oxidation of diaminomaleonitrile

The inhibition of the oligomerization of HCN by montmorillonite clays is shown to be caused by oxidation of diaminomaleonitrile (DAMN) by ferric ion in the clay lattice, with ferrous ion and oxalic acid the reaction products. It is demonstrated that diiminosuccinonitrile is the initial reaction product and is rapidly hydrolized to oxalic acid and HCN. The same oxidative transformations are effected by ferric ion bound to Dowex 50, ferric ion in solution, and Ni(NH3)6(2+). The rate of reaction of DAMN indicates no catalytic role for the clay in the oxidation of DAMN, and little reaction of the latter was observed with montmorillonite in which the bulk of the iron was in the divalent state. The possible significance of these redox reactions to chemical evolution is discussed.

Ferris, J. P.

The role of phosphates in chemical evolution.

The hypohydrous thermal reaction between inorganic phosphates and nucleoside was investigated. The products of the reactions have been identified, and an attempt has been made to determine the mechanism. It was found that orthophosphates can be readily converted into condensed phosphates which are effective phosphorylating agents. Thermal polymerization of inorganic orthophosphates at moderate temperature as a general source of polyphosphates might have provided efficient phosphorylation and condensing agents for primordial syntheses.

Ponnamperuma, C.