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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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Oxygen Permeability and Grain-Boundary Diffusion Applied to Alumina Scales

High-temperature oxygen permeability measurements had determined grain-boundary diffusivities (deltaD(sub gb)) in bulk polycrystalline alumina (Wada, Matsudaira, and Kitaoka). They predict that oxygen deltaD(sub gb,O) varies with oxygen pressure as P(O2)(sup -1/6) at low pressure whereas aluminum deltaD(sub gb),Al varies with P(O2)(sup +3/16) at high pressure. These relations were used to evaluate alumina scale growth in terms of diffusivity and grain size. A modified Wagner treatment for dominant inward oxygen growth produces the concise solution: П(sub i) = k(sub p,i)×G(sub i) = 12 deltaD(sub gb,O,int), where П(sub i) is a constant and k(sub p,i) and G(sub i) refer to instantaneous values of the scale parabolic growth constant and grain size, respectively. A commercial FeCrAl(Zr) alloy was oxidized at 1100 to 1400 degC to determine k(sub p,i), interfacial grain size, П, and thus deltaD(sub gb,O,int). The deltaD(sub gb,O,int) values predicted from oxidation at (375 kJ/mole) were about 20 times less than those obtained above (at 298 kJ/mole), but closer than extrapolations from high-temperature bulk measurements. The experimental oxidation results agree with similar FeCrAl(X) studies, especially where both k(sub p,i) and G(sub i) were characterized. This complete approach accounts for temperature-sensitive oxidation effects of grain enlargement, equilibrium interface pressure variation, and grain-boundary diffusivity.

Smialek, James L.↗

Diffusion mechanisms in chemical vapor-deposited iridium coated on chemical vapor-deposited rhenium

Radiation-cooled rocket thruster chambers have been developed which use CVD Re coated with CVD Ir on the interior surface that is exposed to hot combustion gases. The Ir serves as an oxidation barrier which protects the structural integrity-maintaining Re at elevated temperatures. The diffusion kinetics of CVD materials at elevated temperatures is presently studied with a view to the prediction and extension of these thrusters' performance limits. Line scans for Ir and Re were fit on the basis of a diffusion model, in order to extract relevant diffusion constants; the fastest diffusion process is grain-boundary diffusion, where Re diffuses down grain boundaries in the Ir overlayer.

Hamilton, J. C.↗

A diffusion source for sodium and potassium in the atmospheres of Mercury and the moon

Deep grain-boundary diffusion and regolith diffusion through a fractured crust and regolith can account not only for the Na/K ratios observed in the Mercurian and lunar atmospheres, but the large Na abundance enhancement of Mercury over lunar levels. A hot component of Na and K at Mercury is noted to be smaller in proportion to the total abundances of these two constituents than at the moon; this hot component is consistent with a population of meteoritic substances similar to lunar ones, as well as with a surface composition which has undergone no greater K depletion than that of the moon.

Sprague, Ann L.↗

Diffusive crack growth at a bimaterial interface

The diffusional microcrack growth behavior in a bimaterial system is investigated with an aim at estimating service life of advanced ceramic composites under creep-rupture conditions. The crack is assumed to grow via a coupled surface and grain-boundary diffusion under steady state conditions. The tensile stress distribution along the interface ahead of the moving crack tip is solved, and it is found that a new length parameter exists as a scaling factor for which the solution becomes identical to the single phase case when plotted on the nondimensional physical plane. In contrast to the elastic stress solution which shows singularity at the tip, together with oscillatory character away from the tip, the creep stresses have a peak value away from the tip due to a wedging effect and interfacial sliding eliminates stress oscillation resulting in a decoupling between mode I and mode II loading. This solution ties the far-field loading parameter to the crack tip conditions in terms of the unknown crack velocity to give a specific V-K(1) relationship. It is shown that an exponent of 12 in the conventional crack growth power law emerges at the higher applied stress range.

Chuang, Tze-Jer↗

Diffusion processes in Al2O3 scales - Void growth, grain growth, and scale growth

The internal microstructure and growth kinetics of Al2O3 scales on Ni-15Cr-13Al (wt percent) are investigated by TEM and analyzed in relation to models of diffusivity. Polished arc-melted specimens were oxidized in 1-atm air at 1100 C for 0.1, 1.0, and 20 hours and ion-thinned for TEM at 100 kV. The frequency distribution of void size and grain size is determined for different oxidation times and scale depths. The kinetics of microvoid growth and of grain and scale growth are plotted and related via simplified models to lattice and grain-boundary oxygen diffusivity, respectively. Good agreement is found between model predictions and data obtained by Oishi and Kingery (1960) on oxygen diffusion in bulk Al2O3. The further implications and limitations of these findings are discssed.

Smialek, J. L.↗

Design principles for high efficiency small-grain polysilicon solar cells, with supporting experimental studies

Design principles suggested here aim toward high conversion efficiency (greater than 15 percent) in polysilicon cells. The principles seek to decrease the liabilities of both intragranular and grain-boundary-surface defects. The advantages of a phosphorus atom concentration gradient in a thin (less than 50 microns) base of a p(+)/n(x)/n(+) drift-field solar cell, which produces favorable gradients in chemical potential, minority-carrier mobility and diffusivity, and recombination lifetime (via phosphorus gettering) are suggested. The degrading effects of grain boundaries are reduced by these three gradients and by substituting atoms (P, H, F or Li) for vacancies on the grain-boundary surface. From recent experiments comes support for the benefits of P diffusion down grain boundaries and, for quasi-grain-boundary-free and related structures. New analytic solutions for the n(x)-base include the effect of a power-law dependence between P concentration and lifetime. These provide an upper-bound estimate on the open circuit voltage. Finite-difference numerical solutions of the six Shockley equations furnish complete information about all solar-cell parameters and add insight concerning design.

Lindholm, F. A.↗

The platinum microelectrode/Nafion interface - An electrochemical impedance spectroscopic analysis of oxygen reduction kinetics and Nafion characteristics

The objectives of this study were to use electrochemical impedance spectroscopy (EIS) to study the oxygen-reduction reaction under lower humidification conditions than previously studied. The EIS technique permits the discrimination of electrode kinetics of oxygen reduction, mass transport of O2 in the membrane, and the electrical characteristics of the membrane. Electrode-kinetic parameters for the oxygen-reduction reaction, corrosion current densities for Pt, and double-layer capacitances were calculated. The production of water due to electrochemical reduction of oxygen greatly influenced the EIS response and the electrode kinetics at the Pt/Nafion interface. From the finite-length Warburg behavior, a measure of the diffusion coefficient of oxygen in Nafion and diffusion-layer thickness was obtained. An analysis of the EIS data in the high-frequency domain yielded membrane and interfacial characteristics such as ionic conductivity of the membrane, membrane grain-boundary capacitance and resistance, and uncompensated resistance.

Parthasarathy, Arvind↗

Effects Of Aging On Embrittlement By Hydrogen

Report discusses study of grain-boundary fracture of hydrogen-charged nickel under conditions in which hydrogen is immobile. Thermally-charged nickel specimens aged at several temperatures for various periods of time to allow hydrogen to diffuse. Specimens then quenched and tested in liquid nitrogen (at temperature of 77 K) so distribution of hydrogen produced by aging maintained.

Lassila, D. H.↗

Mechanisms limiting the performance of large grain polycrystalline silicon solar cells

The open-circuit voltage and short-circuit current of large-grain (1 to 10 mm grain diameter) polycrystalline silicon solar cells is determined by the minority-carrier diffusion length within the bulk of the grains. This was demonstrated by irradiating polycrystalline and single-crystal (Czochralski) silicon solar cells with 1 MeV electrons to reduce their bulk lifetime. The variation of short-circuit current with minority-carrier diffusion length for the polycrystalline solar cells is identical to that of the single-crystal solar cells. The open-circuit voltage versus short-circuit current characteristic of the polycrystalline solar cells for reduced diffusion lengths is also identical to that of the single-crystal solar cells. The open-circuit voltage of the polycrystalline solar cells is a strong function of quasi-neutral (bulk) recombination, and is reduced only slightly, if at all, by grain-boundary recombination.

Culik, J. S.↗