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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 289 records · Page 16

Electron escape depth variation in thin SiO2 films measured with variable photon energy

A double crystal monochromator at the Stanford Synchrotron Radiation Laboratory is used to study the Si/SiO2 interface, using photon energies of hv = 1950-3700 eV. This photon energy range allows interfaces to be observed through oxide layers 50 A thick or more. Variations in electron escape depth and/or oxide density as a function of distance from the interface are observed over the entire kinetic energy range (100-3600 eV). These differences are attributed to a strained oxide layer near the interface.

Hecht, M. H.↗

Electrochemical behavior of a titanium electrode in hydrazine solutions

The kinetics of the establishment of the oxidation-reduction potential of a titanium electrode upon contact with hydrazine was studied in different media: H2SO4, NaOH, and Na2SO4. It was found that the nature of the potential shift depends little on the medium. The initial potential determines the rate of potential displacement upon contact with hydrazine, which is explained by the different condition of the electrode's surface.

Levchenko, A. K.↗

Oxygen production by electrolysis of molten lunar regolith

The goal of this study was threefold. First, the theoretical energy requirements of the process were to be defined. This includes studies of the relevant oxidation-reduction reactions in the melt, their kinetics and energies of reaction, and experimental determination of production efficiencies and melt resistivities as functions of melt composition and applied potential. Second, the product(s) of silicate electrolysis were to be characterized. This includes: (1) evaluating the phase relationships in the systems SiO2-TiO2-Al2O3-MgO-FeO-CaO and Fe-Si; (2) estimating the compositions of the metal products as a function of applied potential and feedstock composition based on phase equilibria in the Fe-Si system and free energy values for SiO2 and FeO reported in the literature; (3) definition of compositions of products in actual experiments; and (4) definition of the form the product takes (whether phases separate or remain fixed, whether crystals settle or float in the remaining melt, and how large crystals form). Third, materials for these highly corrosive high-temperature silicate melts were to be identified. This includes identifing materials that may be either inert or thermodynamically stable in these melts, and experimental testing of the materials to confirm that they do not deteriorate. The results are discussed within this framework.

Haskin, Larry A.↗

Mission Cycle Life Prediction for C/SiC Composites

The residual strength and life of C/SiC is dominated by carbon interface and fiber oxidation if thermal and mechanical stresses combine with thermal expansion mismatch in a manner such that seal coat and matrix cracks are open to allow oxygen ingress. Under these circumstances life can be predicted by simple oxidation based models based on reaction controlled kinetics at low temperature and gas phase diffusion controlled kinetics at high temperature. Key life governing variables in these models include temperature, applied stress, initial strength, oxygen partial pressure and total pressure. In this paper these models are described and extended to mission cycle life prediction.

Levine, Stanley R.↗

Shock tube study of the fuel structure effects on the chemical kinetic mechanisms responsible for soot formation, part 2

Soot formation in oxidation of allene, 1,3-butadiene, vinylacetylene and chlorobenzene and in pyrolysis of ethylene, vinylacetylene, 1-butene, chlorobenzene, acetylen-hydrogen, benzene-acetylene, benzene-butadiene and chlorobenzene-acetylene argon-diluted mixtures was studied behind reflected shock waves. The results are rationalized within the framework of the conceptual models. It is shown that vinylacetylene is much less sooty than allene, which indicates that conjugation by itself is not a sufficient factor for determining the sooting tendency of a molecule. Structural reactivity in the context of the chemical kinetics is the dominant factor in soot formation. Detailed chemical kinetic modeling of soot formation in pyrolysis of acetylene is reported. The main mass growth was found to proceed through a single dominant route composed of conventional radical reactions. The practically irreversible formation reactions of the fused polycyclic aromatics and the overshoot by hydrogen atom over its equilibrium concentration are the g-driving kinetic forces for soot formation.

Frenklach, M.↗

Radiolytic Gas-Driven Cryovolcanism in the Outer Solar System

Water ices in surface crusts of Europa, Enceladus, Saturn's main rings, and Kuiper Belt Objects can become heavily oxidized from radiolytic chemical alteration of near-surface water ice by space environment irradiation. Oxidant accumulations and gas production are manifested in part through observed H2O2 on Europa. tentatively also on Enceladus, and found elsewhere in gaseous or condensed phases at moons and rings of Jupiter and Saturn. On subsequent chemical contact in sub-surface environments with significant concentrations of primordially abundant reductants such as NH3 and CH4, oxidants of radiolytic origin can react exothermically to power gas-driven cryovolcanism. The gas-piston effect enormously amplifies the mass flow output in the case of gas formation at basal thermal margins of incompressible fluid reservoirs. Surface irradiation, H2O2 production, NH3 oxidation, and resultant heat, gas, and gas-driven mass flow rates are computed in the fluid reservoir case for selected bodies. At Enceladus the oxidant power inputs are comparable to limits on nonthermal kinetic power for the south polar plumes. Total heat output and plume gas abundance may be accounted for at Enceladus if plume activity is cyclic in high and low "Old Faithful" phases, so that oxidants can accumulate during low activity phases. Interior upwelling of primordially abundant NH3 and CH4 hydrates is assumed to resupply the reductant fuels. Much lower irradiation fluxes on Kuiper Belt Objects require correspondingly larger times for accumulation of oxidants to produce comparable resurfacing, but brightness and surface composition of some objects suggest that such activity may be ongoing.

Cooper, John F.↗

Prediction of hydrodynamics and chemistry of confined turbulent methane-air flames with attention to formation of oxides of nitrogen

A formulation of the governing partial differential equations for fluid flow and reacting chemical species in a tubular combustor is presented. A numerical procedure for the solution of the governing differential equations is described, and models for chemical equilibrium and chemical kinetics calculations are presented. The chemical equilibrium model is used to characterize the hydrocarbon reactions. The chemical kinetics model is used to predict the concentrations of the oxides of nitrogen. The combustor consists of a cylindrical duct of varying cross sections with concentric streams of gaseous fuel and air entering the duct at one end. Four sample cases with specified inlet and boundary conditions are considered, and the results are discussed

Elghobashi, S.↗

The Effect of Electrolyte Additives upon the Lithium Kinetics of Li-Ion Cells Containing MCMB and LiNi(x)Co(1-x)O2 Electrodes and Exposed to High Temperatures

With the intent of improving the performance of lithium-ion cells at high temperatures, we have investigated the use of a number of electrolyte additives in experimental MCMB- Li(x)Ni(y)Co(1-y)O2 cells, which were exposed to temperatures as high as 80 C. In the present work, we have evaluated the use of a number of additives, namely vinylene carbonate (VC), dimethyl acetamide (DMAc), and mono-fluoroethylene carbonate (FEC), in an electrolyte solution anticipated to perform well at warm temperature (i.e., 1.0M LiPF6 in EC+EMC (50:50 v/v %). In addition, we have explored the use of novel electrolyte additives, namely lithium oxalate and lithium tetraborate. In addition to determining the capacity and power losses at various temperatures sustained as a result of high temperature cycling (cycling performed at 60 and 80 C), the three-electrode MCMB-Li(x)Ni(y)Co(1-y)O2 cells (lithium reference) enabled us to study the impact of high temperature storage upon the solid electrolyte interphase (SEI) film characteristics on carbon anodes (MCMB-based materials), metal oxide cathodes, and the subsequent impact upon electrode kinetics.

High Temperture Resilience↗

Symposium (International) on Combustion, 23rd, Universite d'Orleans, France, July 22-27, 1990, Proceedings

The present symposium on combustion discusses reaction kinetics, NO(x) kinetics, premixed, diffusion, and nonsteady flames, turbulent combustion, hazardous waste, fluidized bed combustion, coal boilers and furnaces, engines, heterogeneous kinetics, heterogeneous, droplet, and microgravity combustion, and high-temperature synthesis. Attention is given to reactions of biphenyl, methylnaphthalenes, and phenanthrene with atomic oxygen in the gas phase, the oxidation of ortho-xylene, the effects of water on combustion kinetics at high pressure, and the formation and measurement of N2O in combustion systems. Topics addressed include large ions in premixed benzene-oxygen flames, the structure and kinetics of CH4/N2O flames, the propagation of unsteady hydrogen premixed flames near flammability limits, and the basic structure of lean propane flames. Also considered are OH measurements of piloted diffusion flames of nitrogen-diluted methane near extinction, waste combustion, preferential oxidation of carbon surfaces, and reburning mechanisms in a pulverized coal combustor.

Source record↗

Sintering Characteristics of Multilayered Thermal Barrier Coatings Under Thermal Gradient and Isothermal High Temperature Annealing Conditions

Pyrochlore oxides have most of the relevant attributes for use as next generation thermal barrier coatings such as phase stability, low sintering kinetics and low thermal conductivity. One of the issues with the pyrochlore oxides is their lower toughness and therefore higher erosion rate compared to the current state-of-the-art TBC material, yttria (6 to 8 wt%) stabilized zirconia (YSZ). In this work, sintering characteristics were investigated for novel multilayered coating consisted of alternating layers of pyrochlore oxide viz Gd2Zr2O7 and t' low k (rare earth oxide doped YSZ). Thermal gradient and isothermal high temperature (1316 C) annealing conditions were used to investigate sintering and cracking in these coatings. The results are then compared with that of relevant monolayered coatings and a baseline YSZ coating.

Thermal Barrier Coatings↗

Effects of Hydrogen Annealing, Sulfur Segregation and Diffusion on the Cyclic Oxidation Resistance of Superalloys: a Review

This review is based on the phenomenon of improved oxide scale adhesion for desulfurized superalloys. The proposed adhesion mechanism involves sulfur interfacial segregation and scale-metal bond weakening. Sulfur surface segregation on superalloys is examined as a function of temperature and sulfur content and related to classical behavior predicted by the McLean isotherm. Effective desulfurization to less than 1 ppmw can be accomplished by hydrogen annealing and is governed by sulfur diffusion kinetics in nickel. Hydrogen annealing results in excellent cyclic oxidation resistance for a number of advanced superalloys. The concept of a critical sulfur content is discussed in terms of practical annealing conditions and section thicknesses.

Smialek, J. L.↗

Effects of hydrogen annealing, sulfur segregation and diffusion on the cyclic oxidation resistance of superalloys: A review

This review is based on the phenomenon of improved oxide scale adhesion for desulfurized superalloys. The proposed adhesion mechanism involves sulfur interfacial segregation and scale-metal bond weakening. Sulfur surface segregation on superalloys is examined as a function of temperature and sulfur content, and is related to the classical behavior predicted by the McLean isotherm. Effective desulfurization to less than 1 ppmw can be accomplished by hydrogen annealing and is described by sulfur diffusion kinetics in nickel. Hydrogen annealing results in excellent cyclic oxidation resistance for a number of advanced superalloys. The concept of a critical sulfur content is discussed in terms of practical annealing conditions and section thicknesses.

Smialek, J. L.↗

Orientation Effects in ZnO Films Using Off-Axis Sputtering Deposition

ZnO is a wide-band-gap oxide material and has been used in numerous applications. It is also a good substrate for fabricating GaN-based (a blue laser candidate) devices. Off-axis sputtering technique is one of the best techniques in synthesizing oxide materials because negative ion bombardment and particle kinetic energy is greatly reduced when adatoms condense on substrates. Since the sputtered material from the target arrive on the substrate surface at a 90 deg. configuration, which differs from the normal sputtering geometry, it is expected that the film uniformity and composition distributions will be affected. However, the details of these properties and mechanisms have not been well studied. ZnO films are synthesized on (0001) sapphire and quartz substrates by off-axis sputtering deposition in various oxygen/argon mixture ratios and pressures at different temperatures. Substrates and sputtering sources are placed at three different orientations that are orthogonal to each other. The normal direction of a substrate is parallel to the gravity vector and the other is perpendicular to it. Film thickness profiles at different growth orientations are determined using a profimeter. All films grown at high temperatures have highly textured structures on quartz substrates and epitaxially grow on sapphire substrates. Because of this process, the film surface is very smooth. X-ray diffraction, scanning probe microscopy, and Fourier transfer infrared spectroscopy, and electrical measurements will be used to characterize these films. Detailed results will be discussed in the presentation.

Zhu, Shen↗

Perchlorate on Mars - Overview and Implications

Perchlorate was first detected on Mars by the Wet Chemistry Laboratory (WCL) instrument on the Phoenix lander at a concentration of ~0.5 wt% in northern plains soils. Since that initial detection, perchlorate (and likely chlorate) have been detected on Mars by both surface and orbital instruments. Perchlorate (ClO4-) is an oxidized chlorine compound and salts of perchlorate are kinetically stable (though very reactive at high temperature), very soluble, deliquescent, and have low eutectic temperature (which decreases the temperature for stable liquids on Mars). Chlorate (ClO3-) salts are similar, though they are less kinetically stable than perchlorates. Because many of the analytical signatures of perchlorate and chlorate are similar to the instruments we have used on Mars, we cannot always determine which species is present, so we will use the more generic term “oxychlorine” when referring to perchlorate and/or chlorate.

Archer, P. D.↗

Kinetic limitations on the diffusional control theory of the ablation rate of carbon.

It is shown that the theoretical maximum oxidation rate is limited in many cases even at temperatures much higher than 1650 deg K, not by oxygen transport, but by the kinetics of the carbon-oxygen reaction itself. Mass-loss rates have been calculated at air pressures of 0.01 atm, 1 atm, and 100 atm. It is found that at high temperatures the rate of the oxidation reaction is much slower than has generally been assumed on the basis of a simple linear extrapolation of Scala's 'fast' and 'slow' rate expressions. Accordingly it cannot be assumed that a transport limitation inevitably must be reached at high temperatures.

Maahs, H. G.↗

ESR Analysis of Polymer Photo-Oxidation

Electron-spin resonance identifies polymer-degradation reactions and their kinetics. New technique enables derivation of kinetic model of specific chemical reactions involved in degradation of particular polymer. Detailed information provided by new method enables prediction of aging characteristics long before manifestation of macroscopic mechanical properties.

Kim, Soon Sam↗

Oxidation of dissolved iron under warmer, wetter conditions on Mars: Transitions to present-day arid environments

The copious deposits of ferric-iron assemblages littering the surface of bright regions of Mars indicate that efficient oxidative weathering reactions have taken place during the evolution of the planet. Because the kinetics of atmosphere-surface (gas-solid) reactions are considerably slower than chemical weathering reactions involving an aqueous medium, most of the oxidation products now present in the martian regolith probably formed when groundwater flowed near the surface. This paper examines how chemical weathering reactions were effected by climatic variations when warm, wet environments became arid on Mars. Analogies are drawn with hydrogeochemical and weathering environments on the Australian continent where present-day oxidation of iron is occurring in acidic ground water under arid conditions.

Burns, R. G.↗