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At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
NASA NTRS1981

Electromagnetic studies of redox systems for energy storage

Both chromium and iron couples were studied on various electrode surfaces in acidic perchlorate solution by using rotating ring-disk techniques. It was found that chloride which forms inner sphere coordination complexes with the redox species enhances the electrode kinetics dramatically. The effects of lead underpotential deposition and surface alloy formation on the kinetics of the chromium couple on gold were studied using both linear sweep voltammetry and potential step techniques. The lad underpotential deposition was found to slow down the kinetics of the reduction of the Cr species on gold surfaces although increase the hydrogen overvoltage. The effect on the chromium kinetics can be explained in terms of principally a double layer effect. The underpotential deposition lead species with its positive charge results in a decrease in the concentration of the Cr species at the electrode surface. Similar phenomena were also observed with bismuth underpotential deposition on gold for the iron couple.

Wu, C. D.↗
NASA NTRS1997

Kinetics and Thermochemistry of Reversible Adduct Formation in the Reaction of Cl((sup 2)P(sub J)) with CS2

Reversible adduct formation in the reaction of Cl((sup 2)P(sub J)) with CS2 has been observed over the temperature range 193-258 K by use of time-resolved resonance fluorescence spectroscopy to follow the decay of pulsed-laser-generated Cl((sup 2)P(sub J)) into equilbrium with CS2Cl. Rate coefficients for CS2Cl formation and decomposition have been determined as a function of temperature and pressure; hence, the equilbrium constant has been determined as a function of temperature. A second-law analysis of the temperature dependence of Kp and heat capacity corrections calculated with use of an assumed CS2Cl structure yields the following thermodynamic parameters for the association reaction: Delta-H(sub 298) = -10.5 +/- 0.5 kcal/mol, Delta-H(sub 0) = -9.5 +/- 0.7 kcal/mol, Delta-S(sub 298) = -26.8 +/- 2.4 cal/mol.deg., and Delta-H(sub f,298)(CS2Cl) = 46.4 +/- 0.6 kcal/mol. The resonance fluorescence detection scheme has been adapted to allow detection of Cl((sup 2)P(sub J)) in the presence of large concentrations of O2, thus allowing the CS2Cl + Cl + O2 reaction to be investigated. We find that the rate coefficient for CS2Cl + O2 reaction via all channels that do not generate Cl((sup 2)P(sub J)) is less than 2.5 x 10(exp-16) cu cm/(molecule.s) at 293 K and 300-Torr total pressure and that the total rate coefficient is less than 2 x 10 (exp -15) cu cm/(molecule.s) at 230 K and 30-Torr total pressure. Evidence for reversible adduct formation in the reaction of Cl((sup 2)P(sub J)) with COS was sought but not observed, even at temperatures as low as 194 K.

Nicovich, J. M.↗
NASA NTRS2000

Measurements and Modeling of Nitric Oxide Formation in Counterflow, Premixed CH4/O2/N2 Flames

Laser-induced fluorescence (LIF) measurements of NO concentration in a variety of CH4/O2/N2 flames are used to evaluate the chemical kinetics of NO formation. The analysis begins with previous measurements in flat, laminar, premixed CH4/O2/N2 flames stabilized on a water-cooled McKenna burner at pressures ranging from 1 to 14.6 atm, equivalence ratios from 0.5 to 1.6, and volumetric nitrogen/oxygen dilution ratios of 2.2, 3.1 and 3.76. These measured results are compared to predictions to determine the capabilities and limitations of the comprehensive kinetic mechanism developed by the Gas Research Institute (GRI), version 2.11. The model is shown to predict well the qualitative trends of NO formation in lean-premixed flames, while quantitatively underpredicting NO concentration by 30-50%. For rich flames, the model is unable to even qualitatively match the experimental results. These flames were found to be limited by low temperatures and an inability to separate the flame from the burner surface. In response to these limitations, a counterflow burner was designed for use in opposed premixed flame studies. A new LIF calibration technique was developed and applied to obtain quantitative measurements of NO concentration in laminar, counterflow premixed, CH4/O2/N2 flames at pressures ranging from 1 to 5.1 atm, equivalence ratios of 0.6 to 1.5, and an N2/O2 dilution ratio of 3.76. The counterflow premixed flame measurements are combined with measurements in burner-stabilized premixed flames and counterflow diffusion flames to build a comprehensive database for analysis of the GRI kinetic mechanism. Pathways, quantitative reaction path and sensitivity analyses are applied to the GRI mechanism for these flame conditions. The prompt NO mechanism is found to severely underpredict the amount of NO formed in rich premixed and nitrogen-diluted diffusion flames. This underprediction is traced to uncertainties in the CH kinetics as well as in the nitrogen oxidation chemistry. Suggestions are made which significantly improve the predictive capability of the GRI mechanism in near-stoichiometric, rich, premixed flames and in atmospheric-pressure, diffusion flames. However, the modified reaction mechanism is unable to model the formation of NO in ultra-rich, premixed or in high-pressure, nonpremixed flames, thus indicating the need for additional study under these conditions.

Thomsen, D. Douglas↗
NASA NTRS1979

Crystallization, flow and thermal histories of lunar and terrestrial compositions

Contents: a kinetic treatment of glass formation; effects of nucleating heterogeneities on glass formation; glass formation under continuous cooling conditions; crystallization statistics; kinetics of crystal nucleation; diffusion controlled crystal growth; crystallization of lunar compositions; crystallization between solidus and liquidus; crystallization on reheating a glass; temperature distributions during crystallization; crystallization of anorthite and anorthite-albite compositions; effect of oxidation state on viscosity; diffusive creep and viscous flow; high temperature flow behavior of glass-forming liquids, a free volume interpretation; viscous flow behavior of lunar compositions; thermal history of orange soil material; breccias formation by viscous sintering; viscous sintering; thermal histories of breccias; solute partitioning and thermal history of lunar rocks; heat flow in impact melts; and thermal histories of olivines.

Uhlmann, D. R.↗
NASA NTRS1993

Was Martian mantle wet? A possible consequence of rapid core formation

Degassing of H2O in the planetary interior possibly plays an important role in the evolution of surface environment as well as geologic activity on the terrestrial planets. Mars may be such a planet that well preserves the materials and the geologic features directly related to early evolution of H2O. H2O content in the interior of proto-Mars during accretion and also core formation were investigated. Geodetic data shows that Mars has a dense core. The existence of iron-rich core on Mars may be also supported by the depletion of siderophile elements in SNC meteorites assuming that these samples came from Mars. Isotope systematics of these meteorites indicate that the core formation occurred very early, probably concurrently with Mars formation. Considering the kinetics of metal segregation from silicate, the melting of silicate is likely to precede the core formation. Once the core formation occurs, substantial amount of gravitational energy is released and thus the planetary interior is heated. This energy may be large enough to keep the silicate material in partially molten state along with the accretional heating. Under such circumstances, the silicate melt probably migrates to the surface. Early crustal formation, therefore, is also likely to be associated with the core formation.

Kuramoto, Kiyoshi↗
NASA NTRS1974

Trapping of hydrogen atoms in X-irradiated salts at room temperature and the decay kinetics

The salts (hypophosphites, formates, a phosphite, a phosphate, and an oxalate) were X-irradiated, whereby hydrogen formed chemically by a radiolytic process becomes trapped in the solid. By room temperature vacuum extraction, the kinetics for the evolution of this trapped hydrogen was studied mass spectrometrically. All salts except two exhibited second-order kinetics. The two exceptions (NaH2PO2(H2O) and K2HPO4) showed first-order kinetics. Based on experimental results, the escape of hydrogen involves three steps: the diffusion of hydrogen atoms from the bulk to the surface, association of these atoms on the surface (rate controlling step for second-order hydrogen evolution), and the desorption of molecular hydrogen from the surface. The hydrogen does not escape if the irradiated salt is stored in air, apparently because adsorbed air molecules occupy surface sites required in the escape mechanism.

May, C. E.↗
NASA NTRS1971

The kinetics of crystallization of molten binary and ternary oxide systems and their application to the origination of high modulus glass fibers

Emphasis on the consideration of glass formation on a kinetic process made it possible to think of glass compositions different from those normally employed in the manufacture of glass fibers. Approximately 450 new glass compositions were prepared and three dozen of these compositions have values for Young's modulus measured on bulk specimens greater than nineteen million pounds per square inch. Of the new glasses about a hundred could be drawn into fibers by mechanical methods at high speeds. The fiber which has a Young's modulus measured on the fiber of 18.6 million pounds per square inch and has been prepared in quantity as a monofilament (to date more than 150 million lineal feet of 0.2 to 0.4 mil fiber have been produced). This fiber has also been successfully incorporated both in epoxy and polyimide matrices. The epoxy resin composite has shown a modulus forty percent better than that achievable using the most common grade of competitive glass fiber, and twenty percent better than that obtainable with the best available grade of competitive glass fiber. Other glass fibers of even higher modulus have been developed.

Bacon, J. F.↗
NASA NTRS1996

Were kinetics of Archean calcium carbonate precipitation related to oxygen concentration?

Archean carbonates commonly contain decimetre- to metre-thick beds consisting entirely of fibrous calcite and neomorphosed fibrous aragonite that precipitated in situ on the sea floor. The fact that such thick accumulations of precipitated carbonate are rare in younger marine carbonates suggests an important change in the modes of calcium carbonate precipitation through time. Kinetics of carbonate precipitation depend on the concentration of inhibitors to precipitation that reduce crystallization rates and crystal nuclei formation, leading to kinetic maintenance of supersaturated solutions. Inhibitors also affect carbonate textures by limiting micrite precipitation and promoting growth of older carbonate crystals on the sea floor. Fe2+, a strong calcite-precipitation inhibitor, is thought to have been present at relatively high concentrations in Archean seawater because oxygen concentrations were low. The rise in oxygen concentration at 2.2-1.9 Ga led to the removal of Fe2+ from seawater and resulted in a shift from Archean facies, which commonly include precipitated beds, to Proterozoic facies, which contain more micritic sediment and only rare precipitated beds.

Non-NASA Center↗
NASA NTRS1993

On high-temperature formation of iron-rich olivine in the early solar system

A kinetic restriction on the formation of fayalite-rich olivine in equilibrium with the cooling solar-composition gas appears to exist at the low temperature of approximately 500 K. We offer a high-temperature formation mechanism (different from simple condensation) which operates at high hydrogen depletion (up to 300 times) relative to solar abundance. We show how the necessary depletion rate decreases with temperature (thermodynamical equilibrium is suggested). The consequences for planet formation are considered.

Dorofeyeva, V. A.↗
NASA NTRS2004

Predicting the Atmospheric Composition of Extrasolar Giant Planets

To date, approximately 120 planet-sized objects have been discovered around other stars, mostly through the radial-velocity technique. This technique can provide information about a planet s minimum mass and its orbital period and distance; however, few other planetary data can be obtained at this point in time unless we are fortunate enough to find an extrasolar giant planet that transits its parent star (i.e., the orbit is edge-on as seen from Earth). In that situation, many physical properties of the planet and its parent star can be determined, including some compositional information. Our prospects of directly obtaining spectra from extrasolar planets may improve in the near future, through missions like NASA's Terrestrial Planet Finder. Most of the extrasolar giant planets (EGPs) discovered so far have masses equal to or greater than Jupiter's mass, and roughly 16% have orbital radii less than 0.1 AU - extremely close to the parent star by our own Solar-System standards (note that Mercury is located at a mean distance of 0.39 AU and Jupiter at 5.2 AU from the Sun). Although all EGPs are expected to have hydrogen-dominated atmospheres similar to Jupiter, the orbital distance can strongly affect the planet's temperature, physical, chemical, and spectral properties, and the abundance of minor, detectable atmospheric constituents. Thermochemical equilibrium models can provide good zero-order predictions for the atmospheric composition of EGPs. However, both the composition and spectral properties will depend in large part on disequilibrium processes like photochemistry, chemical kinetics, atmospheric transport, and haze formation. We have developed a photochemical kinetics, radiative transfer, and 1-D vertical transport model to study the atmospheric composition of EGPs. The chemical reaction list contains H-, C-, O-, and N-bearing species and is designed to be valid for atmospheric temperatures ranging from 100-3000 K and pressures up to 50 bar. Here we examine the effect of stellar distance (e.g., incident ultraviolet flux, atmospheric temperature) on the chemical properties of EGPs. The model is applied to two generic Class II and III intermediate temperature EGPs located at 3.3 and 0.27 AU from a solar-like parent star, and the results are compared with a model for Jupiter at 5.2 AU.

Sharp, A. G.↗
NASA NTRS1980

Chemical kinetic models for combustion of hydrocarbons and formation of nitric oxide

The formation of nitrogen oxides NOx during combustion of methane, propane, and a jet fuel, JP-4, was investigated in a jet stirred combustor. The results of the experiments were interpreted using reaction models in which the nitric oxide (NO) forming reactions were coupled to the appropriate hydrocarbon combustion reaction mechanisms. Comparison between the experimental data and the model predictions reveals that the CH + N2 reaction process has a significant effect on NO formation especially in stoichiometric and fuel rich mixtures. Reaction models were assembled that predicted nitric oxide levels that were in reasonable agreement with the jet stirred combustor data and with data obtained from a high pressure (5.9 atm (0.6 MPa)), prevaporized, premixed, flame tube type combustor. The results also suggested that the behavior of hydrocarbon mixtures, like JP-4, may not be significantly different from that of pure hydrocarbons. Application of the propane combustion and nitric oxide formation model to the analysis of NOx emission data reported for various aircraft gas turbines showed the contribution of the various nitric oxide forming processes to the total NOx formed.

Jachimowski, C. J.↗
NASA NTRS2015

Los Alamos RAGE Simulations of the HAIV Mission Concept

The mitigation of potentially hazardous objects (PHOs) can be accomplished by a variety of methods including kinetic impactors, gravity tractors and several nuclear explosion options. Depending on the available lead time prior to Earth impact, non- nuclear options can be very effective at altering a PHOs orbit. However if the warning time is short nuclear options are generally deemed most effective at mitigating the hazard. The NIAC mission concept for a nuclear mission has been presented at several meetings, including the last PDC (2013).We use the adaptive mesh hydrocode RAGE to perform detailed simulations of this Hypervelocity Asteroid Intercept Vehicle (HAIV) mission concept. We use the RAGE code to simulate the crater formation by the kinetic impactor as well as the explosion and energy coupling from the follower nuclear explosive device (NED) timed to detonate below the original surface to enhance the energy coupling. The RAGE code has been well validated for a wide variety of applications. A parametric study will be shown of the energy and momentum transfer to the target 100 m diameter object: 1) the HAIV mission as planned; 2) a surface explosion and 3) a subsurface (contained) explosion; both 2) and 3) use the same source energy as 1).Preliminary RAGE simulations show that the kinetic impactor will carve out a surface crater on the object and the subsequent NED explosion at the bottom of the crater transfers energy and momentum to the target effectively moving it off its Earth crossing orbit. Figure 1 shows the initial (simplified) RAGE 2D setup geometry for this study. Figure 2 shows the crater created by the kinetic impactor and Figure 3 shows the time sequence of the energy transfer to the target by the NED.

Asteroid Mitigation↗
NASA NTRS1995

Grain formation around carbon stars. 1: Stationary outflow models

Asymptotic giant branch (AGB) stars are known to be sites of dust formation and undergo significant mass loss. The outflow is believed to be driven by radiation pressure on grains and momentum coupling between the grains and gas. While the physics of shell dynamics and grain formation are closely coupled, most previous models of circumstellar shells have treated the problem separately. Studies of shell dynamics typically assume the existence of grains needed to drive the outflow, while most grain formation models assume a constant veolcity wind in which grains form. Furthermore, models of grain formation have relied primarily on classical nucleation theory instead of using a more realistic approach based on chemical kinetics. To model grain formation in carbon-rich AGB stars, we have coupled the kinetic equations governing small cluster growth to moment equations which determine the growth of large particles. Phenomenological models assuming stationary outflow are presented to demonstrate the differences between the classical nucleation approach and the kinetic equation method. It is found that classical nucleation theory predicts nucleation at a lower supersaturation ratio than is predicted by the kinetic equations, resulting in significant differences in grain properties. Coagulation of clusters larger than monomers is unimportant for grain formation in high mass-loss models but becomes more important to grain growth in low mass-loss situations. The properties of the dust grains are altered considerably if differential drift velocities are ignored in modeling grain formation. The effect of stellar temperature, stellar luminosity, and different outflow velocities are investigated. The models indicate that changing the stellar temperature while keeping the stellar luminosity constant has little effect on the physical parameters of the dust shell formed. Increasing the stellar luminosity while keeping the stellar temperature constant results in large differences in grain properties. For small outflow velocities, grains form at lower supersaturation ratios and close to the stellar photosphere, resulting in larger but fewer grains. The reverse is true when grains form under high outflow velocities, i.e., they form at higher supersaturation ratios, farther from the star, and are much smaller but at larger quantities.

Egan, Michael P.↗
NASA NTRS1975

Predicted exhaust emissions from a methanol and jet fueled gas turbine combustor

A computer model of a gas turbine combustor has been used to predict the kinetic combustion and pollutant formation processes for methanol and simulated jet fuel. Use of the kinetic reaction mechanisms has also allowed a study of ignition delay and flammability limit of these two fuels. The NOX emissions for methanol were predicted to be from 69 to 92% lower than those for jet fuel at the same equivalence ratio which is in agreement with experimentally observed results. The high heat of vaporization of methanol lowers both the combustor inlet mixture temperatures and the final combustion temperatures. The lower combustion temperatures lead to low NOX emissions while the lower inlet mixture temperatures increase methanol's ignition delay. This increase in ignition delay dictates the lean flammability limit of methanol to be 0.8, while jet fuel is shown to combust at 0.4.

Adelman, H. G.↗
NASA NTRS1983

Glass formation - A contemporary view

The process of glass formation is discussed from several perspectives. Particular attention is directed to kinetic treatments of glass formation and to the question of how fast a given liquid must be cooled in order to form a glass. Specific consideration is paid to the calculation of critical cooling rates for glass formation, to the effects of nucleating heterogeneities and transients in nucleation on the critical cooling rates, to crystallization on reheating a glass, to the experimental determination of nucleation rates and barriers to crystal nucleation, and to the characteristics of materials which are most conducive to glass formation.

Uhlmann, D. R.↗
NASA NTRS1994

Kinetic and mechanistic analysis of dinucleotide and oligonucleotide formation from the 5'-phosphorimidazolide of adenosine on Na(+)-montmorillonite

The rate constants for the condensation reaction of the 5'-phosphorimidazolide of adenosine (ImpA) to form dinucleotides and oligonucleotides have been measured in the presence of Na(+)-volclay (a Na(+)-montmorillonite) in pH 8 aqueous solution at 25 degrees C. The rates of the reaction of ImpA with an excess of adenosine 5'-monophosphoramidate (NH2pA), P1,P2-diadenosine 5',5'-pyrophosphate (A5'ppA), or adenosine 5'-monophosphate (5'-AMP or pA) in the presence of the montmorillonite to form NH2pA3'pA, A5'ppA3'pA, and pA3'pA, respectively, were measured. Only 3',5'-linked products were observed. The magnitude of the rate constants decrease in the order NH2pA3'pA > A5'-ppA3'pA > pA3'pA. The binding of ImpA to montmorillonite was measured, and the adsorption isotherm was determined. The binding of ImpA to montmorillonite and the formation of higher oligonucleotides is not observed in the absence of salts. Mg2+ enhances binding and oligonucleotide formation more than Ca2+ and Na+. The rate constants for the oligonucleotide formation were determined from the reaction products formed from 10 to 40 mM ImpA in the presence of Na(+)-montmorillonite using the computer program SIMFIT. The magnitudes of the rate constants for the formation of oligonucleotides increased in the order 2-mer < 3-mer < 4-mer ... 7-mer. The rate constants for dinucleotide and trinucleotide formation are more than 1000 times larger than those measured in the absence of montmorillonite. The rate constants for the formation of dinucleotide, trinucleotide, and tetranucleotide are 41,2.6, and 3.7 times larger than those for the formation of oligo(G)s with a poly(C) template. The hydrolysis of ImpA was accelerated 35 times in the presence of the montmorillonite. The catalytic ability of montmorillonite to form dinucleotides and oligonucleotides is quantitatively evaluated and possible pathways for oligo(A) formation are proposed.

NASA Discipline Exobiology↗
NASA NTRS2014

Formation of Fe/mg Smectite Under Acidic Conditions from Synthetic Adirondack Basaltic Glass: an Analog to Fe/mg Smectite Formation on Mars

Smectite has been detected as layered material hundreds of meters thick, in intracrater depositional fans, in plains sediments, and deposits at depth on Mars. If early Mars hosted a dense CO2 atmosphere, then extensive carbonate should have formed in the neutral/alkaline conditions expected for smectite formation. However, large carbonate deposits on Mars have not been discovered. Instead of neutral to moderately alkaline conditions, early Mars may have experienced mildly acidic conditions that allowed for Fe/Mg smectite formation but prevented widespread carbonate formation. The objective of this work is to demonstrate that Fe(II)/Mg saponite and nontronite can form in mildly acidic solutions (e.g., pH 4). Synthetic basaltic glass (< 53 microns) of Adirondack rock class composition was exposed to pH 4 (acetic acid buffer) and N2 purged (anoxic) solutions amended with 0 and 10 mM Mg or Fe(II). Basaltic glass in these solutions was heated to 200 C in batch reactors for 1, 7, and 14 days. X-ray diffraction analysis of reacted materials detected the presence of phyllosilicates as indicated by a approx. 15.03-15.23Angstroms (001) peak. Smectite was confirmed as the phyllosilicate after treatments with glycerol and KCl and heating to 550 C. Trioctahedral saponite was confirmed by the presence of a 4.58 to 4.63 Angstroms (02l) and 1.54Angstroms (060) peaks. Saponite concentration was highest, as indicated by XRD peak intensity, in the 10 mM Mg treatment followed by the 0 mM and then 10 mM Fe(II) treatments. This order of sapontite concentration suggests that Fe(II) additions may have a role in slowing the kinetics of saponite formation relative to the other treatments. Nontronite synthesis was attempted by exposing Adirondack basaltic glass to pH 4 oxic solutions (without N2 purge) at 200 C for 14 days. X-ray diffraction analysis indicated that mixtures of trioctahedral (saponite) and dioctahedral (nontronite) may have formed in these experiments based on the 02l and 060 peaks. Moessbauer analysis coupled with future experiments are planned to verify if nontronite can be formed under mildly acidic and oxic conditions. Results of this work demonstrate that acidic conditions could have occurred on an early Mars, which allowed for smectite formation but inhibited carbonate formation.

Sutter, B.↗