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NASA NTRS1991

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.↗

NASA NTRS1991

Domain-decomposed preconditionings for transport operators

The performance was tested of five different interface preconditionings for domain decomposed convection diffusion problems, including a novel one known as the spectral probe, while varying mesh parameters, Reynolds number, ratio of subdomain diffusion coefficients, and domain aspect ratio. The preconditioners are representative of the range of practically computable possibilities that have appeared in the domain decomposition literature for the treatment of nonoverlapping subdomains. It is shown that through a large number of numerical examples that no single preconditioner can be considered uniformly superior or uniformly inferior to the rest, but that knowledge of particulars, including the shape and strength of the convection, is important in selecting among them in a given problem.

Chan, Tony F.↗

NASA NTRS1991

Magnetism and superconductivity of some Tl-Cu oxides

Many copper oxide based Thallium compounds are now known. In comparison to the Bi-compounds, the Tl-system shows a richer diversity; i.e., High Temperature Superconductors (HTSC) can be obtained with either one or two Tl-0 layers (m = 1,2); also, the triple-digit phases are easier to synthesize. The value of d, oxygen stoichiometry, is critical to achieving superconductivity. The Tl system is robust to oxygen loss; Tl may be lost or incorporated by diffusion. A diffusion coefficient equal to 10 ms at 900 C was determined. Both ortho-rhombic and tetragonal structures are found, but HTSC behavior is indifferent to the crystal symmetry. This system has the highest T(sub c) confirmed. T(sub c) generally increases with p, the number of CuO layers, but tends to saturate at p = 3. Zero resistance was observed at temperatures as great as 125 K. Most of these HTSC's are hole type, but the Ce-doped specimens may be electronic. The magnetic aspects were studied; because in addition to defining the perfectly diamagnetic ground state as in conventional superconductors, magnetism of the copper oxides show a surprising variety. This is true of both the normal and the superconducting states. Also, due to the large phonon contribution to the specific heat at the high T(sub c) jump, electronic density of states, D(Ef), and coherence length are uncertain, and thus, are estimated from the magnetic results. Results from the Tl-system CuO, LaBaCuO,120 and the Bi-CuO compounds are discussed. The emphasis is on the role of magnetism in the Tl-CuO HTSC, but technological aspects are also pointed out.

Datta, Timir↗

NASA NTRS1991

Voyager 2 electron observations in the magnetosphere of Neptune

This paper describes electron data obtained during the Neptune encounter by the Voyager 2 plasma science experiment. The densities and temperatures of low-energy (10-5950 eV) electrons and the electrostatic potential of the spacecraft near Neptune are derived. The data indicate that the escape of charged particles from Triton and the local ionization of atoms in the neutral torus originating from Triton are the major plasma sources. It is inferred that this neutral torus of hydrogen atoms has a density of about 300/cu cm and an inner boundary at 8 R(N). The data near Neptune exhibit signatures suggesting that both precipitation into Neptune's atmosphere and ring absorption are important plasma loss mechanisms. Plasma transport in the magnetosphere appears to be very fast; the diffusion coefficient is 1 x 10 exp -7 L exp 3 R(N) exp 2/sec.

Zhang, Ming↗

NASA NTRS1991

Transport of N2O in the stratosphere related to the equatorial semiannual oscillation

The double-peak structure observed in the distribution of N2O during the spring equinoctial condition is studied by means of a 2D time-dependent tracer model. The meridional transport circulation is determined from computed diabatic heating rates, and the horizontal eddy diffusion coefficients are computed as residuals by potential vorticity conservation, using observed mean winds to compute the budget of zonal mean potential vorticity. This model is used to predict the 30-d evolution of the observed N2O field. The integrated results are generally in good agreement with observed tracer fields up to the midstratosphere. It is proposed that standard climatologies underestimate the strength of the equatorial semiannual oscillation in the zonal mean wind and temperature fields.

Choi, Woo Kap↗

NASA NTRS1992

Tidal evolution of globular clusters. I - Method

Tidal evolution of globular clusters is regulated by both Galactic tidal effects and internal relaxation processes. In order to investigate the tidal evolution of globular clusters, a numerical scheme which utilizes a Fokker-Planck approach as well as direct numerical integration of the restricted three-body problem is developed. In the inner regions of the cluster, stellar orbits are mapped with the cluster's gravitational potential and orbit-averaged diffusion coefficients. In the outer regions, the Galactic tidal field is explicitly included in the direct orbital integration. This method is presented here with some tests on King-Michie models.

Oh, K. S.↗

NASA NTRS1992

Flow-induced gelation of living (micellar) polymers

The effect of shear velocity gradients on the size (L) of rodlike micelles in dilute and semidilute solution is considered. A kinetic equation is introduced for the time-dependent concentration of aggregates of length L, consisting of 'bimolecular' combination processes L + L-prime yield (L + L-prime) and unimolecular fragmentations L yield L + (L - L-prime). The former are described by a generalization (from spheres to rods) of the Smoluchowski mechanism for shear-induced coalesence of emulsions, and the latter by incorporating the tension-deformation effects due to flow. Steady-state solutions to the kinetic equation are obtained, with the corresponding mean micellar size evaluated as a function of the Peclet number P (i.e., the dimensionless ratio of the flow rate and the rotational diffusion coefficient). For sufficiently dilute solutions, only a weak dependence of the micellar size on P is found. In the semidilute regime, however, an apparent divergence in the micellar size at P of about 1 suggests a flow-induced first-order gelation phenomenon.

Bruinsma, Robijn↗

NASA NTRS1992

On the interplanetary cosmic ray latitudinal gradient

Results are presented from measurements, from 1983 to 1990, of the temporal history of the latitudinal and radial gradients of cosmic ray particles with E greater than 70-MeV. The data used include measurements obtained by the Voyager 2 and Pioneer 10 spacecraft near the heliographic equatorial plane, and from Pioneer 11 and Voyager 1 at average latitudes of 16 deg and 30 deg, respectively. Using the data from Pioneer 11 and Voyager 1 at different altitudes, the altitude dependence of the 26-day-average differential cosmic ray latitudinal gradient was deduced. The gradient was found to be a strong function of latitude when the tilt angle approached zero and became essentially independent of latitude for tilt angles above 30 deg. The relationship between the latitudinal and radial gradients was used to estimate the perpendicular diffusion coefficient for E greater than 7-MeV particles.

Lockwood, J. A.↗

NASA NTRS1992

Hydrocarbons and eddy mixing in Neptune's atmosphere

The most recent analysis of the Voyager ultraviolet solar occultation observations at Neptune indicates a methane mixing ratio 1-10 times above saturation in the lower stratosphere, unlike the value of 500-1000 times saturation which was suggested just before the encounter of Voyager with Neptune. The acetylene mixing ratio in the 0.1 mb region is found to be (6-8) x 10 exp -8, which is approximately a factor of 3 lower than the value reported in our Voyager/Science paper. The eddy diffusion coefficient at the homopause (1-3) x 10 exp 7 sq cm/s, is found to be more like that of Saturn than Uranus. The new results on CH4, C2H2 and K have strong implications for the stratospheric temperatures, now warmer, and the source of heating. Furthermore, the pre-Voyager models of the hydrocarbon hazes need to be revised in view of the new model atmosphere.

Atreya, S. K.↗

NASA NTRS1992

Cosmic-ray-modified supernova remnant shocks

The evolution of cosmic-ray-modified SNRs during the early Sedov phase is investigated using the time-dependent, two-fluid model for diffusive shock acceleration. Consideration is given to the sensitivity of net acceleration efficiency to model assumptions regarding density structure of the external medium as well as time dependence in the diffusion coefficient and the cosmic-ray adiabatic index. Of the model assumptions explored, the greatest sensitivity was found to time variations in the specific heat ratio to cosmic rays. It was found that if tau is greater than or approximately equal to few times 100, dynamically significant cosmic-ray pressures are produced early in the Sedov inefficient cosmic-ray accelerators. For the SNR models under consideration, the total energy channeled into the cosmic rays can be of order 10 percent of the initial blast energy for both the uniform density and inverse-square density interstellar medium models.

Jones, T. W.↗

NASA NTRS1992

Temperature dependence of the electrode kinetics of oxygen reduction at the platinum/Nafion interface - A microelectrode investigation

Results of a study of the temperature dependence of the oxygen reduction kinetics at the Pt/Nafion interface are presented. This study was carried out in the temperature range of 30-80 C and at 5 atm of oxygen pressure. The results showed a linear increase of the Tafel slope with temperature in the low current density region, but the Tafel slope was found to be independent of temperature in the high current density region. The values of the activation energy for oxygen reduction at the platinum/Nafion interface are nearly the same as those obtained at the platinum/trifluoromethane sulfonic acid interface but less than values obtained at the Pt/H3PO4 and Pt/HClO4 interfaces. The diffusion coefficient of oxygen in Nafion increases with temperature while its solubility decreases with temperature. These temperatures also depend on the water content of the membrane.

Parthasarathy, Arvind↗

NASA NTRS1992

The effect of tensile stress on hydrogen diffusion in metal alloys

The effect of tensile stress on hydrogen diffusion has been determined for Type 303 stainless steel, A286 CRES, and Waspaloy and IN100 nickel-base alloys. It was found that hydrogen diffusion coefficients are not significantly affected by stress, while the hydrogen permeabilities are greatly affected in Type 303 stainless steel and A286 CRES (iron-based alloys), but are affected little in Waspaloy (nickel-base) and not affected in all in IN100 (nickel base). These observations might be taken as an indication that hydrogen permeabilities are affected by stress in iron-based alloys, but only slightly affected in nickel-based alloys. However, it is too early to make such a generalization based on the study of only these four alloys.

Danford, M. D.↗

NASA NTRS1993

New parameterizations and sensitivities for simple climate models

This paper presents a reexamination of the earth radiation budget parameterization of energy balance climate models in light of data collected over the last 12 years. The study consists of three parts: (1) an examination of the infrared terrestrial radiation to space and its relationship to the surface temperature field on time scales from 1 month to 10 years; (2) an examination of the albedo of the earth with special attention to the seasonal cycle of snow and clouds; (3) solutions for the seasonal cycle using the new parameterizations with special attention to changes in sensitivity. While the infrared parameterization is not dramatically different from that used in the past, the albedo in the new data suggest that a stronger latitude dependence be employed. After retuning the diffusion coefficient the simulation results for the present climate generally show only a slight dependence on the new parameters. Also, the sensitivity parameter for the model is still about the same (1.25 C for a 1 percent increase of solar constant) for the linear models and for the nonlinear models that include a seasonal snow line albedo feedback (1.34 C). One interesting feature is that a clear-sky planet with a snow line albedo feedback has a significantly higher sensitivity (2.57 C) due to the absence of smoothing normally occurring in the presence of average cloud cover.

Graves, Charles E.↗

NASA NTRS1992

A quantitative assessment of the role of the post-shock turbulent region in the formation of Forbush decreases

We present results of a survey of the relation between Forbush decreases, magnetic clouds, and interplanetary shocks during the period August 1978 to November 1982. We have used data from the ISEE-3 study of bidirectional ions associated with magnetic structures or clouds of Marsden et al. (1987), and ground-based observations of Forbush decreases from several neutron monitors. We use the two-step model of a Forbush decrease. We assume that the first step is due to the passage of the postshock turbulent region, and that the second is due to the passage of the magnetic cloud or structure which usually follows the postshock turbulent region. To determine the effectiveness of the postshock turbulent region in causing a Forbush decrease, we have evaluated the radial diffusion coefficient of the postshock turbulent region for the eight largest events during the above period using observations of the magnetic field. We have made a quantitative assessment of the relative importance of the postshock turbulent region in the formation of the Forbush decrease, concluding that the postshock turbulent region alone is not sufficient to cause a Forbush decrease.

Sanderson, T. R.↗

NASA NTRS1993

A solar dynamo surface wave at the interface between convection and nonuniform rotation

A simple dynamo surface wave is presented to illustrate the basic principles of a dynamo operating in the thin layer of shear and suppressed eddy diffusion beneath the cyclonic convection in the convection zone of the sun. It is shown that the restriction of the shear delta(Omega)/delta(r) to a region below the convective zone provides the basic mode with a greatly reduced turbulent diffusion coefficient in the region of strong azimuthal field. The dynamo takes on the character of a surface wave tied to the lower surface z = 0 of the convective zone. There is a substantial body of evidence suggesting a fibril state for the principal flux bundles beneath the surface of the sun, with fundamental implications for the solar dynamo.

Parker, E. N.↗

NASA NTRS1993

Coherent fiber optic sensor for early detection of cataractogenesis in a human eye lens

A lensless backscatter fiber optic probe is used to measure the size distribution of protein molecules inside an excised, but intact, human eye lens. The fiber optic probe, about 5 mm in diameter, can be positioned arbitrarily close to the anterior surface of the eye; it is a trans-receiver, which delivers a Gaussian laser beam into a small region inside the lens and provides a coherent detection of the laser light scattered by the protein molecules in the backward direction. Protein sizes determined from the fast and slow diffusion coefficients show good correlation with the age of the lens and cataractogenesis.

Dhadwal, Harbans S.↗

NASA NTRS1991

Finite linear diffusion model for design of overcharge protection for rechargeable lithium batteries

The overcharge condition in secondary lithium batteries employing redox additives for overcharge protection has been theoretically analyzed in terms of a finite linear diffusion model. The analysis leads to expressions relating the steady-state overcharge current density and cell voltage to the concentration, diffusion coefficient, standard reduction potential of the redox couple, and interelectrode distance. The model permits the estimation of the maximum permissible overcharge rate for any chosen set of system conditions. The model has been experimentally verified using 1,1-prime-dimethylferrocene as a redox additive. The theoretical results may be exploited in the design and optimization of overcharge protection by the redox additive approach.

Narayanan, S. R.↗

NASA NTRS1992

Co diffusion and growth of buried single-crystal CoSi2 in Si(111) by endotaxy

At a growth temperature of 800 C, Co deposited on a Si capping layer exhibits oriented growth on buried CoSi2 grains on Si(111), a process referred to as endotaxy. This occurs preferentially to surface nucleation of CoSi2, provided the thickness of the Si cap is less than a critical value of about 100 nm for deposition rates of 0.003-0.01 nm/s. The steady-state process is modeled using known values of the Co diffusion coefficient and solid solubility in Si, allowing some conclusions to be drawn regarding parameters relevant to CoSi2 epitaxy. Using this technique, single-crystal continuous layers of CoSi2 can be formed under a high-quality Si capping layer.

Fathauer, R. W.↗