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All sourcesNASA NTRSDOE OSTI
NASA NTRS2005

Improved Anode for a Direct Methanol Fuel Cell

A modified chemical composition has been devised to improve the performance of the anode of a direct methanol fuel cell. The main feature of the modified composition is the incorporation of hydrous ruthenium oxide into the anode structure. This modification can reduce the internal electrical resistance of the cell and increase the degree of utilization of the anode catalyst. As a result, a higher anode current density can be sustained with a smaller amount of anode catalyst. These improvements can translate into a smaller fuel-cell system and higher efficiency of conversion. Some background information is helpful for understanding the benefit afforded by the addition of hydrous ruthenium oxide. The anode of a direct methanol fuel cell sustains the electro-oxidation of methanol to carbon dioxide in the reaction CH3OH + H2O--->CO2 + 6H(+) + 6e(-). An electrocatalyst is needed to enable this reaction to occur. The catalyst that offers the highest activity is an alloy of approximately equal numbers of atoms of the noble metals platinum and ruthenium. The anode is made of a composite material that includes high-surface-area Pt/Ru alloy particles and a proton-conducting ionomeric material. This composite is usually deposited onto a polymer-electrolyte (proton-conducting) membrane and onto an anode gas-diffusion/current-collector sheet that is subsequently bonded to the proton-conducting membrane by hot pressing. Heretofore, the areal density of noble-metal catalyst typically needed for high performance has been about 8 mg/cm2. However, not all of the catalyst has been utilized in the catalyzed electro-oxidation reaction. Increasing the degree of utilization of the catalyst would make it possible to improve the performance of the cell for a given catalyst loading and/or reduce the catalyst loading (thereby reducing the cost of the cell). The use of carbon and possibly other electronic conductors in the catalyst layer has been proposed for increasing the utilization of the catalyst by increasing electrical connectivity between catalyst particles. However, the relatively low density of carbon results in thick catalyst layers that impede the mass transport of methanol to the catalytic sites. Also, the electrical conductivity of carbon is less than 1/300th of typical metals. Furthermore, the polymer-electrolyte membrane material is acidic and most metals are not chemically stable in contact with it. Finally, a material that conducts electrons (but not protons) does not contribute to the needed transport of protons produced in the electro-oxidation reaction.

Valdez, Thomas↗
NASA NTRS1990

Study of diamond film growth and properties

The objective was to study diamond film growth and its properties in order to enhance the laser damage threshold of substrate materials. Calculations were performed to evaluate laser induced thermal stress parameter, R(sub T) of diamond. It is found that diamond has several orders of magnitude higher in value for R(sub T) compared to other materials. Thus, the laser induced damage threshold (LIDT) of diamond is much higher. Diamond films were grown using a microwave plasma enhanced chemical vapor deposition (MPECVD) system at various conditions of gas composition, pressure, temperature, and substrate materials. A 0.5 percent CH4 in H2 at 20 torr were ideal conditions for growing of high quality diamond films on substrates maintained at 900 C. The diamond films were polycrystalline which were characterized by scanning electron microscopy (SEM) and Raman scattering spectroscopy. The top surface of the growing film is always rough due to the facets of polycrystalline film while the back surface of the film replicates the substrate surface. An analytical model based on two dimensional periodic heat flow was developed to calculate the effective in-plane (face parallel) diffusivity of a two layer system. The effective diffusivity of diamond/silicon samples was measured using a laser pulse technique. The thermal conductivity of the films was measured to be 13.5 W/cm K, which is better than that of a type Ia natural diamond. Laser induced damage experiments were performed on bare Si substrates, diamond film coated Si, and diamond film windows. Significant improvements in the LIDT were obtained for diamond film coated Si compared to the bare Si.

Albin, Sacharial↗
NASA NTRS1985

Vacuum MOCVD fabrication of high efficience cells

Vacuum metal-organic-chemical-vapor-deposition (MOCVD) is a new fabrication process with improved safety and easier scalability due to its metal rather than glass construction and its uniform multiport gas injection system. It uses source materials more efficiently than other methods because the vacuum molecular flow conditions allow the high sticking coefficient reactants to reach the substrates as undeflected molecular beams and the hot chamber walls cause the low sticking coefficient reactants to bounce off the walls and interact with the substrates many times. This high source utilization reduces the materials costs power device and substantially decreases the amounts of toxic materials that must be handled as process effluents. The molecular beams allow precise growth control. With improved source purifications, vacuum MOCVD has provided p GaAs layers with 10-micron minority carrier diffusion lengths and GaAs and GaAsSb solar cells with 20% AMO efficiencies at 59X and 99X sunlight concentration ratios. Mechanical stacking has been identified as the quickest, most direct and logical path to stacked multiple-junction solar cells that perform better than the best single-junction devices. The mechanical stack is configured for immediate use in solar arrays and allows interconnections that improve the system end-of-life performance in space.

Partain, L. D.↗
NASA NTRS2018

Relative Sputtering Rates of FeS, MgS, and Mg Silicates: Implications for ISM Gas Phase Depletions of Rock-Forming Elements

Astronomical measurements of S abundances in the diffuse interstellar medium (ISM) indicate ionized S is a dominant species with little (< 5%) S residing in grains (e.g. Jenkins 2009). This is an enigmatic result, given that abundant Fe-sulfide grains are observed in dust around pre- and post-main sequence stars and are also observed as major components of primitive meteoritic and cometary samples. These disparate observations suggest that the lifetime of sulfide grains in the ISM is short because of destruction processes. Our previous work has shown that FeS and MgS retain their crystallinity and do not amorphize during radiation processing, whereas enstatite and forsterite are readily amorphized. We have extended this study to measure the relative sputtering rates of FeS and MgS compared to enstatite and forsterite. Irradiation of FeS with 4 keV He+ results in preferential sputtering of S and the formation of a thin 2-3 nm, compact Fe metal layer that armors the surface. The zone of S loss extends to a depth of ~8-10 nm below the exposed surface. Despite this S loss, the FeS retains its crystallinity and shows no sign of incipient amorphization. Irradiation of FeS with 5kV Ga+ in a focused ion beam (FIB) instrument resulted in preferential sputtering of S and the formation of a 5-8-nm thick surface layer of nanophase Fe metal. X-ray mapping shows that the zone of S sputtering extends to a depth of nearly 20 nm, but there is no evidence for FeS amorphization, consistent with our previous work. The irradiation experiments show that the relative sputtering rate of FeS and MgS are much higher than olivine or enstatite. Sputtering experiments utilizing 30 kV and 5 kV Ga ions in the FIB produced volume loss in troilite that was ~4X greater than in enstatite or forsterite. The sputter yield under these conditions is such that for every Si atom sputtered from enstatite, ~14 S atoms are sputtered from FeS. We have performed similar sputtering experiments on Fe-bearing niningerite (MgS) and co-existing enstatite from the ALH 84170 EH3 chondrite. MgS also sputters much more rapidly than enstatite with a relative Si:S sputter yield of 1:8. For MgS, sulfur is highly depleted at the surface and the S-depletion zone extends to a depth of ~15 nm (using 5 kV Ga+). There is a corresponding zone of Mg and especially Fe enrichment that extends from 5 to ~10 nm below the surface, respectively. The dominant grain destruction mechanism in the ISM is sputtering from passage of supernova-generated shock waves. This process also results in the amorphization of crystalline silicates in the ISM. Our results indicate that FeS and MgS grains produced in evolved stars and injected into the ISM will be destroyed more rapidly than crystalline silicates. This process may account for the lack of significant depletion of S from the gas phase in the ISM. However, rare nanophase FeS grains occur as inclusions in circumstellar amorphous silicate grains found in comet dust particles analyzed in the laboratory. These results show that a finite amount of S in the ISM is sequestered in solid grains.

SPUTTERING RATES↗
NASA NTRS2002

Linear Temporal Stability Analysis of a Low-Density Round Gas Jet Injected into a High-Density Gas

It has been observed in previous experimental studies that round helium jets injected into air display a repetitive structure for a long distance, somewhat similar to the buoyancy-induced flickering observed in diffusion flames. In order to investigate the influence of gravity on the near-injector development of the flow, a linear temporal stability analysis of a round helium jet injected into air was performed. The flow was assumed to be isothermal and locally parallel; viscous and diffusive effects were ignored. The variables were represented as the sum of the mean value and a normal-mode small disturbance. An ordinary differential equation governing the amplitude of the pressure disturbance was derived. The velocity and density profiles in the shear layer, and the Froude number (signifying the effects of gravity) were the three important parameters in this equation. Together with the boundary conditions, an eigenvalue problem was formulated. Assuming that the velocity and density profiles in the shear layer to be represented by hyperbolic tangent functions, the eigenvalue problem was solved for various values of Froude number. The temporal growth rates and the phase velocity of the disturbances were obtained. The temporal growth rates of the disturbances increased as the Froude number was reduced (i.e. gravitational effects increased), indicating the destabilizing role played by gravity.

Lawson, Anthony L.↗
NASA NTRS1972

Gas Surface Interactions Occurring on Materials Within Ultrahigh Vacuum

The physical adsorption of nitrogen on the chemically cleaned surfaces of Pyrex, 347 stainless steel and polycrystalline nickel was investigated over the pressure range 1 x 10 to the minus 12th power to 3 x 10 to the minus 7th power torr and for temperatures 77.4 and 87.4 K. The adsorption data were linearized by the Dubinin-Radushkevich equation. The metal surfaces were cleaned by electron impact desorption (EID) and the desorbed gases analyzed by mass spectrometry. Work function measurements were also used to indicate changes in the surface condition following an EID dose. At least a monolayer of gas was observed to desorb from the metal surfaces. The isotherms revealed that the metal surfaces were very heterogeneous and that the Pyrex surface had been leached. The calculated isosteric heats of adsorption indicated that the relative order of the physical binding of nitrogen to the solids was 347 stainless steel Pyrex nickel. A relationship was observed to exist in the dynamic technique between the equilibration time and the pressure above the absorbed layer. The slope of the log-log plot of these parameters was found to be sensitive to the surface heterogeneity and may be related to the activation energy for surface diffusion of physically absorbed molecules.

Outlaw, R. A.↗
NASA NTRS1993

Particle-Gas Dynamics in the Midplane of a Protoplanetary Nebula

In this paper, we study the stage of planetary formation during which the particulate material is still dispersed as centimeter-to-meter sized primordial aggregates. During this stage, particles are able to settle toward the midplane into a layer of mass density comparable to or much greater than that of the gas. Nonlinear, coupled interactions between the particles and the nebula gas become significant and ultimately determine the vertical profiles of the particle density and the mean velocities of the particles and the nearby gas. This is the environment in which the earliest planetesimals probably form. Our numerical models rely on the Reynolds averaged Navier-Stokes equations for the gas and particles and are fully viscous and turbulent (and, for the particles. compressible). Our turbulence modeling uses a Prandtl local shear parametrization, validated by laboratory experiments. We have developed a new model for particle diffusion involving the profile of the nebula gas turbulence and the particle Schmidt number, which is a function of particle size and density. We model a cool, quiescent nebula at 1 AU (280 K) and 10 AU (90 K) and a higher temperature stage (1000 K) at 1 AU. Our main results include: (a) rapid accretion of planetesimals by gravitationally unstable fragmentation on an orbital time scale (the 'Goldreich-Ward instability') is unlikely to occur until objects have already accreted by some other process to the mass of the largest known meteorite samples, if at all; (b) from 'seeds' as small as 10 m, growth of 10- to 100-km planetesimals can proceed rapidly by drift-augmented accretion in the particle-rich midplane with orbital decay of about 1% for the growing planetesimals; (c) outward transport of vapor and small entrained chips can account for significant radial compositional and mineralogical mixing in primitive meteorite parent bodies. Other implications may be drawn concerning particle random collisional velocities and the time scales of midplane turbulence.

Cuzzi, Jeffrey N.↗
NASA NTRS1985

Thermophoretically enhanced mass transport rates to solid and transpiration-cooled walls across turbulent (law-of-the-wall) boundary layers

Convective-diffusion mass transfer rate predictions are made for both solid wall and transpiration-cooled 'law-of-the-wall' nonisothermal turbulent boundary layers (TBLs), including the mechanism of thermophoresis, i.e., small particle mass transport 'down a temperature gradient'. The present calculations are confined to low mass-loading situations but span the entire particle size range from vapor molecules to particles near the onset of inertial ('eddy') impaction. It is shown that, when Sc is much greater than 1, thermophoresis greatly increases particle deposition rates to internally cooled solid walls, but only partially offsets the appreciable reduction in deposition rates associated with dust-free gas-transpiration-cooled surfaces. Thus, efficient particle sampling from hot dusty gases can be carried out using transpiration 'shielded' probe surfaces.

Gokoglu, Suleyman A.↗
NASA NTRS1977

Characteristics of laminar gas jet diffusion flames under the influence of elevated gravity

Laminar gas jet diffusion flames of hydrogen, methane, ethane, and propane, stabilized on small cylindrical burners, were studied at elevated gravity in a centrifuge to investigate the role of buoyancy in such flames. Photographic observation of the hydrocarbon flames indicated that length and carbon luminosity decreased with increasing buoyancy. These flames eventually separated from the burner rim and finally extinguished as gravity increased. Hydrogen flames, however, did not separate or extinguish up to about 31 times earth normal gravity. Length data are reported and interpreted with the aid of a simplified model which describes the flame as a heated vertical cylindrical sheet to which oxygen is supplied by a free convection boundary layer.

Altenkirch, R. A.↗
NASA NTRS2004

Permanent Sequestration of Emitted Gases in the Form of Clathrate Hydrates

Underground sequestration has been proposed as a novel method of permanent disposal of harmful gases emitted into the atmosphere as a result of human activity. The method was conceived primarily for disposal of carbon dioxide (CO2, greenhouse gas causing global warming), but could also be applied to CO, H2S, NOx, and chorofluorocarbons (CFCs, which are super greenhouse gases). The method is based on the fact that clathrate hydrates (e.g., CO2 6H2O) form naturally from the substances in question (e.g., CO2) and liquid water in the pores of sub-permafrost rocks at stabilizing pressures and temperatures. The proposed method would be volumetrically efficient: In the case of CO2, each volume of hydrate can contain as much as 184 volumes of gas. Temperature and pressure conditions that favor the formation of stable clathrate hydrates exist in depleted oil reservoirs that lie under permafrost. For example, CO2-6H2O forms naturally at a temperature of 0 C and pressure of 1.22 MPa. Using this measurement, it has been calculated that the minimum thickness of continuous permafrost needed to stabilize CO2 clathrate hydrate is only about 100 m, and the base of the permafrost is known to be considerably deeper at certain locations (e.g., about 600 m at Prudhoe Bay in Alaska). In this disposal method, the permafrost layers over the reservoirs would act as impermeable lids that would prevent dissociation of the clathrates and diffusion of the evolved gases up through pores.

Duxbury, N.↗
NASA NTRS1972

Mach 1 oxidation of thoriated nickel chromium at 1204 C /2200 F/.

Electropolished and ground samples of TD-NiCr were exposed to a 1-atm, Mach 1 gas stream at 1204 C for times up to 50 hr. The samples were subjected to both cyclic and isothermal exposure. Weight change, metal loss, X-ray diffraction, metallographic, and electron microprobe analyses were performed. Neither surface preparation nor cyclic-against-isothermal-exposure conditions had a strong effect on the oxidation behavior of the alloy. Initially, a Cr2O3 layer was formed whose volatilization resulted in a very rapid loss of metal - more than 40 microns in the first hour. At about 1 hr, the Cr2O3 layer broke down and NiO began to cover the surface. By 5 hr, the NiO had covered the surface and the rate of loss slowed. The rate-controlling step was diffusion of Cr through NiO.

Lowell, C. E.↗
NASA NTRS2004

Simple Two-Dimensional Corrections for One-Dimensional Pulse Tube Models

One-dimensional oscillating flow models are very useful for designing pulse tubes. They are simple to use, not computationally intensive, and the physical relationship between temperature, pressure and mass flow are easy to understand when used in conjunction with phasor diagrams. They do not possess, however, the ability to directly calculate thermal and momentum diffusion in the direction transverse to the oscillating flow. To account for transverse effects, lumped parameter corrections, which are obtained though experiment, must be used. Or two-dimensional solutions of the differential fluid equations must be obtained. A linear two-dimensional solution to the fluid equations has been obtained. The solution provides lumped parameter corrections for one-dimensional models. The model accounts for heat transfer and shear flow between the gas and the tube. The complex Nusselt number and complex shear wall are useful in describing these corrections, with phase relations and amplitudes scaled with the Prandtl and Valensi numbers. The calculated ratio, a, between a two-dimensional solution of the oscillating temperature and velocity and a one-dimensional solution for the same shows a scales linearly with Va for Va less than 30. In this region alpha less than 0.5, that is, the enthalpy flow calculated with a two-dimensional model is 50% of a calculation using a one-dimensional model. For Va greater than 250, alpha = 0.8, showing that diffusion is still important even when it is confined to a thing layer near the tube wall.

Lee, J. M.↗
NASA NTRS2004

A Resonant Pulse Detonation Actuator for High-Speed Boundary Layer Separation Control

A variety of different types of actuators have been previously investigated as flow control devices. Potential applications include the control of boundary layer separation in external flows, as well as jet engine inlet and diffuser flow control. The operating principles for such devices are typically based on either mechanical deflection of control surfaces (which include MEMS flap devices), mass injection (which includes combustion driven jet actuators), or through the use of synthetic jets (diaphragm devices which produce a pulsating jet with no net mass flow). This paper introduces some of the initial flow visualization work related to the development of a relatively new type of combustion-driven jet actuator that has been proposed based on a pulse detonation principle. The device is designed to utilize localized detonation of a premixed fuel (Hydrogen)-air mixture to periodically inject a jet of gas transversely into the primary flow. Initial testing with airflow successfully demonstrated resonant conditions within the range of acoustic frequencies expected for the design. Schlieren visualization of the pulsating air jet structure revealed axially symmetric vortex flow, along with the formation of shocks. Flow visualization of the first successful sustained oscillation condition is also demonstrated for one configuration of the current test section. Future testing will explore in more detail the onset of resonant combustion and the approach to conditions of sustained resonant detonation.

Beck, B. T.↗
NASA NTRS1988

Axisymmetric perturbations of thin gaseous disks. I - Unstable convective modes and their consequences for the solar nebula

The axisymmetric perturbations of a thin, differentially rotating gas disk in which the vertical temperature stratification is superadiabatic are analyzed. The growth rate of adiabatic convective normal modes is calculated, departures from simple polytropic disk models are briefly discussed, and the detailed vertical structure of the eigenfunctions is analyzed. The stabilizing effect of radiative diffusion on convective modes is considered. It is found that rotation and compressibility tend to reduce the rate of growth of the disturbances, and that the growth rate increases without limit and is proportional to the square root of the radial wavenumber in polytropic equilibria. The maximum radial size of convective eddies scales like the square root of the degree of superadiabaticity times the size of the convective zone. There is significant convective penetration into radiatively stable layers only for the fundamental and low-order harmonic modes, whose vertical wavelength is comparable to the size of the convective layer.

Ruden, Steven P.↗
NASA NTRS1996

Fluid Creep Effects on Near-Wall Solute Transport for Non-Isothermal Ampoules

There is a growing practical and theoretical interest in developing accurate macroscopic modelling for flows arising in chemical or physical vapor transport (VT) crystal growth experiments, including those conducted in reduced gravity environments. Rosner was the first person to point out that previously neglected rarefield gas dynamics phenomena (Stefan and bouyancy-driven flows) become rather important sources of convection. In particular, the combination of rarefaction and strong gradients of temperature (and/or concentration) tangential to the side-walls of the ampoule induces convective flows known as thermal (and concentration) 'creep' respectively. His order-of-magnitude estimates revealed that thermal creep effects can be non-negligible even at normal gravitational levels. On the macroscopic level, the bulk fluid mechanics can be adequately described by the familiar macroscopic equations as long as the boundary conditions are modified to account for the integrated effect of kinetic boundary layers adjacent to solid boundaries. Motivated by the growing importance of these phenomena, we have embarked on a series of computational studies to elucidate these fundamental creep-induced effects for a rarefied gas in simple, two-dimensional confined geometries. However, unlike previous related studies, we resort to a microscopic description of the gas, mathematically expressed by the Boltzmann integro-differential equation. We employ the direct simulation Monte Carlo (DSMC) method of Bird, the theoretical foundations and several practical applications. In the case of thermally induced flows, the no-time counter method of Bird is used, as implemented for a hard-sphere gas. The scheme has been also extended to account for realistic molecular interaction models, an extension necessary if the diffusion physics underlying concentration creep are to be captured.

Papadopoulos, Dimitrios↗
NASA NTRS1976

The ionization of a low-density intercloud medium by a single O star

The ionization structure of hydrogen in a cloud-containing low-density gas surrounding an O star is calculated, emphasizing how UV photons cause the ionization of hydrogen in regions which are totally obscured from the star by neutral clouds. Particular consideration is given to the ionization of such obscured regions by diffuse Lyman continuum radiation produced when H(+) recombines directly to the ground state. The assumed physical structure of the cloud-containing neighborhood of an O star is discussed, a method is outlined for expressing the emission and absorption properties of the neutral clouds and their shadows in terms of effective volume emissivities and absorption coefficients on a line of sight, and equations of radiative transfer are derived for diffuse and stellar radiation in a cloud-containing H II region. Reradiation of Lyman continuum photons from the ionized boundary layer of a neutral cloud or shadow is analyzed. The expected emission measure across a large cloud-containing H II region is determined and found to compare well with that obtained from observations of H-alpha emission around runaway O stars. It is shown that the hydrogen in cloud shadows may be completely ionized by diffuse radiation within approximately half the Stroemgren radius, depending on the extent of that radius, the average frequency of the Lyman continuum radiation from the star, and the average cloud size.

Elmegreen, B. G.↗
NASA NTRS2003

Effects of Mean Flow Profiles on Instability of a Low-Density Gas Jet Injected into a High-Density Gas

The objective of this study was to investigate the effects of the mean flow profiles on the instability characteristics in the near-injector region of low-density gas jets injected into high-density ambient gas mediums. To achieve this, a linear temporal stability analysis and a spatio-temporal stability analysis of a low-density round gas jet injected vertically upwards into a high-density ambient gas were performed by assuming three different sets of mean velocity and density profiles. The flow was assumed to be isothermal and locally parallel. Viscous and diffusive effects were ignored. The mean flow parameters were represented as the sum of the mean value and a small normal-mode fluctuation. A second order differential equation governing the pressure disturbance amplitude was derived from the basic conservation equations. The first set of mean velocity and density profiles assumed were those used by Monkewitz and Sohn for investigating absolute instability in hot jets. The second set of velocity and density profiles assumed for this study were the ones used by Lawson. And the third set of mean profiles included a parabolic velocity profile and a hyperbolic tangent density profile. The effects of the inhomogeneous shear layer and the Froude number (signifying the effects of gravity) on the temporal and spatio-temporal results for each set of mean profiles were delineated. Additional information is included in the original extended abstract.

Vedantam, Nanda Kishore↗
NASA NTRS2005

Nebula Models of Non-Equilibrium Mineralogy: Wark-Lovering Rims

Introduction: The meteorite record contains several examples of minerals that would not persist if allowed to come to equilibrium with a cooling gas of solar composition. This includes all minerals in CAIs and AOAs. Their survival is generally ascribed to physical removal of the object from the gas (isolation into a large parent object, or ejection by a stellar wind), but could also result from outward radial diffusion into cooler regions, which we discuss here. Accretion of CAIs into planetesimals has also been relied on to preserve them against loss into the sun. However, this suggestion faces several objections. Simple outward diffusion in turbulence has recently been modeled in some detail, and can preserve CAIs against loss into the sun [2]. Naturally, outward radial diffusion in turbulence is slower than immediate ejection by a stellar wind, which occurs on an orbital timescale. Here we ask whether these different transport mechanisms can be distinguished by nonequilibrium mineralogy, which provides a sort of clock. Our application here is to one aspect of CAI mineralogy - the Wark-Lovering rims (WLR); even more specifically, to alteration of one layer in the WLR sequence from melilite (Mel) to anorthite (An).

Cuzzi, J. N.↗