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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 91 records · Page 5

Effect of ohmic, mass-transfer, and kinetic resistances on linear-sweep voltammetry in a cylindrical-pore electrode

A means is presented to account for the effect of ohmic, mass-transfer, and kinetic resistances on linear-sweep voltammograms by modeling a pore in a porous matrix as a cylindrical-pore electrode, and solving the mass and charge conservation equations in the context of this geometry for the simply redox reaction O + ne(-) yield R where both O and R are soluble species. Both analytical and numerical techniques are used to solve the governing equations. The calculated peak currents and potentials are correlated by empirical formulas to the measurable parameters: sweep rate, concentration of the redox species, diffusion coefficient, conductivity of the electrolyte, and pore dimensions. Using the correlations, a methodology is established for determining if the redox reaction kinetics are irreversible or reversible (Nernstian). If the reaction is irreversible, it is shown how the standard rate constant and the transfer coefficient may be extracted from linear-sweep voltammetry data, or, if the reaction is reversible, how the number of electrons transferred may be deduced.

Weidner, John W.↗

Radiation-Tolerant, SpaceWire-Compatible Switching Fabric

Current and future near-Earth and deep space exploration programs and space defense programs require the development of robust intra-spacecraft serial data transfer electronics that must be reconfigurable, fault-tolerant, and have the ability to operate effectively for long periods of time in harsh environmental conditions. Existing data transfer systems based on state-of-the-art serial data transfer protocols or passive backplanes are slow, power-hungry, and poorly reconfigurable. They provide limited expandability and poor tolerance to radiation effects and total ionizing dose (TID) in particular, which presents harmful threats to modern submicron electronics. This novel approach is based on a standard library of differential cells tolerant to TID, and patented, multi-level serial interface architecture that ensures the reliable operation of serial interconnects without application of a data-strobe or other encoding techniques. This proprietary, high-speed differential interface presents a lowpower solution fully compatible with the SpaceWire (SW) protocol. It replaces a dual data-strobe link with two identical independent data channels, thus improving the system s tolerance to harsh environments through additional double redundancy. Each channel incorporates an automatic line integrity control circuitry that delivers error signals in case of broken or shorted lines.

Katzman, Vladimir↗

Laboratory Studies of Thermal Energy Charge Transfer of Silicon and Iron Ions in Astrophysical Plasmas

The laser ablation/ion storage facility at the UNLV Physics Department is dedicated to the study of atomic processes in low temperature plasmas. Our current program is directed to the study of charge transfer of multiply charged ions and neutrals that are of importance to astrophysics at energies less than 1 eV (about 10(exp 4) K). Specifically, we measure the charge transfer rate coefficient of ions such as N(2+), Si(3+), Si(3+), with helium and Fe(2+) with molecular and atomic hydrogen. All these ions are found in a variety of astrophysical plasmas. Their electron transfer reactions with neutral atoms can affect the ionization equilibrium of the plasma.

Kwong, Victor H. S.↗

Theoretical study of CO chemisorption on nickel and copper surfaces

A comparative study of the chemisorption of CO on Ni(001) and Cu(001) surfaces has been performed. The study is based on an analysis of the electronic structure of (M)5CO clusters obtained from self-consistent field X alpha scattered-wave calculations. The electron orbital formed principally by the 5 sigma orbital on CO was found to be mainly responsible for the bonding of the CO molecule to the metal surface for both the CO/Ni and CO/Cu systems. The different occupation of the antibonding 7 a sub 1 orbital in the two clusters is believed to be the major reason for the large difference observed in the measured heats of adsorption of CO on Ni and Cu surfaces. It was found also that metal atoms transfer electronic charge to the antibonding pi(asterisk)-like orbital of CO. A possible correlation between the amount of the charge transfered and the relative ease of dissociation of CO molecules on metal surfaces is discussed.

Yu, H. L.↗

Oxidation of the Mantle Wedge by H+ in Aqueous Fluids: A New Interdisciplinary Approach

The observation that arc magmas are the most oxidized on Earth have led petrologists to question whether the subduction process might cause oxidation of the sub-arc mantle source. A strong correlation between the input of slab-derived aqueous fluid and Fe3(+)/ΣFe in arc magmas has led to the hypothesis that slab fluids may facilitiate the transfer of redox potential from oxidized slab material to mantle wedge and subsequently to primary arc melts. Despite this intuitive link, identifying an efficient and ubiquitous chemical process to transfer oxidation state in slab fluids has been challenging. Pure H2O alone is an inefficient oxidizer in the mantle, necessitating another oxidant within the fluid. Commonly invoked components include S or C, which are likely heterogeneously distributed within subducting slabs, and direct transfer of Fe3(+), which is only possible in very solute-rich fluids. Here we present a new mechanism to explain the oxidation of the sub-arc mantle by slab-derived aqueous fluid, wherein dissolved H(+)(aq) is reduced to H2(aq). Redox equilibrium is satisfied by electron transfer from Fe2(+)(s), which is oxidized in the rock to Fe3(+)(s) in the reaction: 2Fe2(+)(s) + 2H(+)(aq) = 2Fe3(+)(s) + H2(aq). This simple reaction was previously overlooked due to the assumption that all H must be bound by H2O molecules (i.e., no dissolved H), applicable to a pure H2O fluid, but not one with a solute load as addressed here. The application of thermodynamic modeling tools from aqueous geochemistry (DEW, EQ3/6) to mantle petrology predicts this reaction between mantle rock and slab fluid with our own experimentally constrained chemistry and fO2 (QFM+2). Mass transfer model results show an increase in Fe3(+)/ΣFe in mantle rock from MORB- like (0.15) to arc-like (0.2–0.3) values at reasonable fluid fluxes, co-incident with increasing H2 activity in the fluid. This can explain the stark correlation between slab fluid input into the mantle wedge and the observed fO2 of arc magmas. Moreover, it does not require diffusion of hydrogen out of the system. Instead, H2 remains dissolved in fluid in equilibrium with oxidized mantle rock.

Iacovino, Kayla↗

Front-illuminated CCD with open pinned-phase region and two-phase transfer gate regions

A front-illuminated CCD of relative high quantum efficiency (QE) and high charge transfer efficiency (CTE) utilizes an open-phase region for receiving photons and two-phase gate regions (.phi..sub.1 and .phi..sub.2) for transferring electrons collected in one pixel to the next. The open-phase region is implanted with additional n-type elements (phosphorus) in order to increase the potential of the CCD channel in the open-phase region for collection of electrons and additionally implanted with concentrated and very shallow p-type elements (boron) to pin the surface of the n-channel in the open-phase region to OV, while gate region .phi..sub.1 and .phi..sub.2 are biased to -3.5V and driven to +10V by a two-phase transfer clock. The open pinned-phase (OPP) region thus permits two-phase transfer clocking and optimum reception of photons during the integration periods between transfer clock pulses.

Janesick, James R.↗

Biophysical Characterization of Iron-Sulfur Proteins

Iron-sulfur proteins are primordial catalysts and biological electron carriers that today drive major metabolic pathways across all forms of life. They can access a diversity of oxidation states and can mediate electron transfer over an extended range of reduction potentials spanning more than 1 V. Depending on the protein micro-environment and geometry of ligand, co-ordination the iron-sulfur clusters can occur in different forms [2Fe-2S], [3Fe-4S], HiPIP [4Fe-4S], and [4Fe-4S]. There are several spectroscopic methods available to characterize the composition and electronic configuration of the iron-sulfur clusters, such as optical methods and electron paramagnetic resonance. This paper presents the protocols used to characterize the metal center of Coiled-Coil Iron-Sulfur (CCIS), an artificial metalloprotein containing one [4Fe-4S] cluster. It is expected that these protocols will be of general utility for other iron-sulfur proteins.

Iron-sulfur proteins↗

Solvent-tuned intramolecular charge-recombination rates in a conjugated donor-acceptor molecule

The nonradiative charge-recombination rates from the charge-transfer state of a new conjugated donor-acceptor molecule (p-cyano-p-prime-methylthiodiphenylacetylene) can be tuned over almost an order of magnitude by varying the polarity of the solvent. These measurements of intramolecular recombination show a turnover of rates as a function of emission energy, consistent with the 'normal' and 'inverted' behavior of Marcus theory. Steady-state spectra and time-resolved measurements make it possible to quantitatively compare thermal and optical electron-transfer rates as a function of driving force and demonstrate their correspondence.

Khundkar, Lutfur R.↗

Energy conversion at liquid/liquid interfaces: artificial photosynthetic systems

This chapter focuses on multielectron reactions in organized assemblies of molecules at the liquid/liquid interface. We describe the thermodynamic and kinetic parameters of such reactions, including the structure of the reaction centers, charge movement along the electron transfer pathways, and the role of electric double layers in artificial photosynthesis. Some examples of artificial photosynthesis at the oil/water interface are considered, including water photooxidation to the molecular oxygen, oxygen photoreduction, photosynthesis of amphiphilic compounds and proton evolution by photochemical processes.

Non-NASA Center↗

Epitaxial gallium arsenide wafers

The preparation of GaAs epitaxial layers by a vapor transport process using AsCl3, Ga and H2 was pursued to provide epitaxial wafers suitable for the fabrication of transferred electron oscillators and amplifiers operating in the subcritical region. Both n-n(+) structures, and n(++)-n-n(+) sandwich structures were grown using n(+) (Si-doped) GaAs substrates. Process variables such as the input AsCl3 concentration, gallium temperature, and substrate temperature and temperature gradient and their effects on properties are presented and discussed.

Black, J. F.↗

Integrated material-surface analyzer

These 10 surface-analysis tests can be run without breaking vacuum: secondary-ion mass spectroscopy, ion-scattering spectroscopy, electron-stimulated desorption, residual-gas analysis, auger electron spectroscopy, x-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, characteristic-electron energy-loss spectroscopy, scanning electron microscope, scanning low-energy electron probe. Quadruple mass spectrometer, used in first 4 tests, serves as electron transfer lens in last 6 tests.

Grunthaner, F. J.↗

Facility produced charge-exchange ions

These facility produced ions are created by charge-exchange collisions between neutral atoms and energetic thruster beam ions. The result of the electron transfer is an energetic neutral atom and an ion of only thermal energy. There are true charge-exchange ions produced by collisions with neutrals escaping from the ion thruster and being charge-exchange ionized before the neutral intercepts the tank wall. The facility produced charge-exchange ions will not exist in space and therefore, represent a source of error where measurements involving ion thruster plasmas and their density are involved. The quantity of facility produced ions in a test chamber with a 30 cm mercury ion thruster was determined.

Carruth, M. R., Jr.↗

Sources of background current in the ECC ozonesonde - Implications for total ozone measurements

The source of the background current in the usual operation of the electrochemical concentration cell ozonesonde is the reduction of tri-iodide normally present in the cathode solution. The time variations in the background current can be explained by the slow rates of solution mass transport and of heterogeneous electron transfer for tri-iodide. Oxygen does not contribute to the background current through reaction with iodide to produce tri-iodide. Direct reduction of oxygen at the cathode is negligible once the electrodes have been exposed to iodide for 24 hours. The present background current correction is altitude-dependent, since it is based on an assumed sensitivity of the electrochemical concentration cell to oxygen. If the background current is independent of altitude and of oxygen, a constant, uncorrected, background current of 0.1 microamp would produce an error of +5.5% for the total ozone value of the electrochemical concentration cell for a typical midlatitude total ozone value of 0.345 atm-cm.

Thornton, D. C.↗

Effects of solution mass transport on the ECC ozonesonde background current

Measurement of the mass transport rate constant for the electrochemical concentration cell in an ozonesonde as a function of the pressure is reported. The investigation was performed to accurately model the residual current present in the ECC cell in the absence of ozone. The convective mass transport for two sondes were determined while maintaining a sufficiently negative cathodic potential to eliminate electron transfer at the cathode surface. A sonde was placed in a bell jar and subjected to varying pressure levels. When the background current was kept below 0.1 microamp and pressure was from 100-1000 mb, the necessary correction term for the pressure was independent of pressure. However, below 100 mb, a logarithmic decrease in the background current with pressure is expected. Present practices, involving a sensitivity to oxygen, are calculated to result in overestimation of the total ozone between 1000-10 mb by 0.0096 atm-cm with a background current of 0.1 microamp at 1000 mb.

Thornton, D. C.↗

Electrode kinetics of oxygen reduction - A theoretical and experimental analysis of the rotating ring-disc electrode method

In order to calculate most of the rate constants for the intermediate formation of H2O2 in the electroreduction of O2 to H2O, the theoretical treatments of the rotating ring-disc electrode method by Damjanovic et al. (1966, 1967), Bagotskii et al. (1968, 1969), and Wroblowa et al. (1976) are modified. Rotating ring-disc electrode experimental data obtained for O2 reduction in Pt in 0.55 M H2SO4 are used to illustrate the calculations of rate constants according to the above theoretical treatments. A simple reaction model as proposed by the first author is consistent with the experimental data. The results indicate that O2 (97 percent) reduces to H2O in a direct four-electron transfer reaction. The adsorption of O2 is probably the rate-determining step in the potential region more negative than 0.5 V vs. reversible hydrogen electrode.

Hsueh, K.-L.↗