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At least 235 records · Page 13

Heterogeneous chemistry on liquid sulfate aerosols - A comparison of in situ measurements with zero-dimensional model calculations

The possibility that stratospheric chlorine is converted from reservoir to reactive forms by heterogeneous reactions on background sulfate aerosols is examined. Tightly constrained photochemical models have been used to calculate ClO abundances for the morning and the afternoon conditions observed on January 24, 1989 outside the Arctic polar vortex by instruments on the NASA ER-2 aircraft. Calculations involving gas-phase chemistry only and calculations with heterogeneous chemistry including HCl evaporation from the aerosol both produce ClO abundances that agree with observations; calculations in which HCl removal from the aerosol is controlled by heterogeneous reactions produce ClO abundances that are 3 to 3.5 times larger than observations. These results suggest that HCl evaporation must be included in a model of the chemistry of background aerosols.

Mather, J. H.↗

Reactions of SiC with H2/H2O/Ar mixtures at 1300 C

Thermochemical modeling anticipates the existence of three reaction regions for the case of a sintered alpha-SiC with 5 percent H2/H2O/Ar at 1300 C, depending on the initial water vapor or, equivalently, oxygen, content of the gas stream. While a high oxygen content leads to SiC-protecting SiO2 surface film formation and limits consumption of the SiC through passive oxidation, intermediate oxygen contents lead to SiO and CO formation and rapid SiC consumption. In this intermediate region, reaction rates appear to be controlled by H2O gas-phase transport to the sample; reacted microstructures exhibit extensive grain-boundary attack in this region. Very low oxygen content is predicted to selectively remove carbon, with free silicon formation.

Jacobson, Nathan S.↗

Passivation Of High-Temperature Superconductors

Surfaces of high-temperature superconductors passivated with native iodides, sulfides, or sulfates formed by chemical treatments after superconductors grown. Passivating compounds nearly insoluble in and unreactive with water and protect underlying superconductors from effects of moisture. Layers of cuprous iodide and of barium sulfate grown. Other candidate passivating surface films: iodides and sulfides of bismuth, strontium, and thallium. Other proposed techniques for formation of passivating layers include deposition and gas-phase reaction.

Vasquez, Richard P.↗

Empirical relationships between gas abundances and UV selective extinction

Several studies of gas-phase abundances in lines of sight through the outer edges of dense clouds are summarized. These lines of sight have 0.4 less than E(B-V) less than 1.1 and have inferred spatial densities of a few hundred cm(-3). The primary thrust of these studies has been to compare gaseous abundances in interstellar clouds that have various types of peculiar selective extinction. To date, the most notable result has been an empirical relationship between the CN/Fe I abundance ratio and the depth of the 2200 A extinction bump. It is not clear at the present time, however, whether these two parameters are linearly correlated or the data are organized into two discrete ensembles. Based on 19 samples and assuming the clouds form discrete ensembles, lines of sight that have a CN/Fe I abundance ratio greater than 0.3 (dex) appear to have a shallow 2.57 plus or minus 0.55 bump compared to 3.60 plus or minus 0.36 for other dense clouds and compared to the 3.6 Seaton (1979) average. The difference in the strength of the extinction bump between these two ensembles is 1.03 plus or minus 0.23. Although a high-resolution IUE survey of dense clouds is far from complete, the few lines of sight with shallow extinction bumps all show preferential depletion of certain elements, while those lines of sight with normal 2200 A bumps do not. Ca II, Cr II, and Mn II appear to exhibit the strongest preferential depletion compared to S II, P II, and Mg II. Fe II and Si II depletions also appear to be enhanced somewhat in the shallow-bump lines of sight. It should be noted that Copernicus data suggest all elements, including the so-called nondepletors, deplete in diffuse clouds (Snow and Jenkins 1980, Joseph 1988). Those lines of sight through dense clouds that have normal 2200 A extinction bumps appear to be extensions of the depletions found in the diffuse interstellar medium. That is, the overall level of depletion is enhanced, but the element-to-element abundances are similar to those in diffuse clouds. In a separate study, the abundances of neutral atoms were studied in a dense cloud having a shallow 2200 A bump and in one with a normal strength bump.

Joseph, Charles L.↗

Airborne observations of the infrared emission bands

Earlier airborne studies of the infrared bands between 5 and 8 microns have now been extended to a sample of southern sources selected from the IRAS Low Resolution Spectra (LRS) atlas. The correlation between the strongest bands at 6.2 and 7.7 microns is now based on a total sample of 40 sources and is very strong. A new emission band at 5.2 microns, previously predicted for polycyclic aromatic hydrocarbons (PAHs), is recognized in 27 sources; it too correlates with the dominant 7.7 micron band, showing that the 5.2 micron feature also belongs to the generic spectrum of PAH features at 3.3, 5.6, 6.2, 6.2, 7.7, 8.7, 11.3, and 12.7 microns. Sufficient sources are had now to define the relative strengths of most of these bands in three separate nebular environments: planetaries, H II regions, and reflection nebulae. Significant variations are detected in the generic spectra of PAHs in these different environments which are echoed by variations in the exact wavelength of the strong 7.7 micron peak. The earlier suggestion that, in planetaries, the fraction of total emission observed by IRAS that is carried by the PAH emissions is correlated with nebular gas-phase C/O ratio is supported by the addition of newly-observed southern planetaries, including the unusually carbon-rich (WC10) nebular nuclei. These (WC10) nuclei also exhibit a strong plateau of emission linking the 6.2 and 7.7 micron features.

Cohen, M.↗

The pre- and post-accretion irradiation history of cometary ices

Comets Halley and Wilson exhibited similar 3.4 micron emission features at approx. 1 AU from the Sun. A simple model of thermal emission from organic grains fits the feature, provides optical depths in good agreement with spacecraft measurements, and explains the absence of longer-wavelength organic features as due to spectral heliocentric evolution (Chyba and Sagan, 1987). The model utilizes transmission spectra of organics synthesized in the laboratory by irradiation of candidate cometary ices; the authors have long noted that related gas-phase syntheses yield polycyclic aromatic hydrocarbons, among other organic residues (Sagan et al., 1967). The authors previously concluded (Chyba and Sagan, 1987) that Halley's loss of several meters' depth with each perihelion passage, combined with the good fit of the Halley 3.4 micron feature to that of comet Wilson (Allen and Wickramasinghe, 1987), argues for the primordial - but not necessarily interstellar - origin of cometary organics. The authors examine the relative importance to the formation of organics of the variety of radiation environments experienced by comets. They conclude that there is at present no compelling reason to choose any of three contributing mechanisms (pre-accretion UV, pre-accretion cosmic ray, and post-accretion radionuclide processing) as the most important.

Chyba, Christopher↗

Catalytic ignition model in a monolithic reactor with in-depth reaction

Two transient models have been developed to study the catalytic ignition in a monolithic catalytic reactor. The special feature in these models is the inclusion of thermal and species structures in the porous catalytic layer. There are many time scales involved in the catalytic ignition problem, and these two models are developed with different time scales. In the full transient model, the equations are non-dimensionalized by the shortest time scale (mass diffusion across the catalytic layer). It is therefore accurate but is computationally costly. In the energy-integral model, only the slowest process (solid heat-up) is taken as nonsteady. It is approximate but computationally efficient. In the computations performed, the catalyst is platinum and the reactants are rich mixtures of hydrogen and oxygen. One-step global chemical reaction rates are used for both gas-phase homogeneous reaction and catalytic heterogeneous reaction. The computed results reveal the transient ignition processes in detail, including the structure variation with time in the reactive catalytic layer. An ignition map using reactor length and catalyst loading is constructed. The comparison of computed results between the two transient models verifies the applicability of the energy-integral model when the time is greater than the second largest time scale of the system. It also suggests that a proper combined use of the two models can catch all the transient phenomena while minimizing the computational cost.

Tien, Ta-Ching↗

Droplet-turbulence interactions in subcritical and supercritical evaporating sprays

The objective of this research is to obtain an improved understanding of droplet turbulence interactions in vaporizing liquid sprays under conditions typical of those encountered in liquid fueled rocket engines. The interaction between liquid droplets and the surrounding turbulent gas flow affects droplet dispersion, droplet collisions, droplet vaporization and gas-phase, fuel-oxidant mixing, and therefore has a significant effect on the engine's combustion characteristics. An example of this is the role which droplet-turbulence interactions are believed to play in combustion instabilities. Despite their importance, droplet-turbulence interactions and their effect on liquid fueled rocket engine performance are not well understood. This is particularly true under supercritical conditions, where many conventional concepts, such as surface tension, no longer apply. Our limited understanding of droplet-turbulence interactions, under both subcritical conditions, represents a major limitation in our ability to design improved liquid previously unavailable information and valuable new insights which will directly impact the design of future liquid fueled rocket engines, as well as, allow for the development of significantly improved spray combustion models, making such models useful design tools.

Santavicca, Domenic A.↗

The G value in plasma and radiation chemistry

The application of the G-value concept to plasma chemistry is considered. A general formula which expresses the G value for a general reaction in terms of experimentally controllable parameters is derived by applying simple gas-dynamic theory to a plasma reactor with straight walls. The formula expresses the G value as a function of the electrical power absorbed, the fraction of molecules transformed, and the flow rate of the gas entering the reactor. The formula was applied to the ammonia plasma radio-frequency discharge data of d'Agostino et al. (1981); the results showed that the G(-NH3) value lies in the range of 6.0-20 molecules/100 eV, depending on the conditions. This similarity of the G(-NH3) value with Peterson's (1974) range 2.7-10 found for the gas-phase radiolysis of ammonia, suggests that there might be a common reaction mechanism initiated by inelastic electron-molecule collisions.

Baird, James K.↗

Variations in the abundance of transiently heated particles within nearby molecular clouds

IRAS images of molecular clouds in the Chamaeleon, Taurus, and Ursa Major complexes show that the mid-IR emission from transiently heated particles is distributed very differently from the 100 micron emission from large dust grains. The ratio between 12 and 100 micron emission varies by more than one order of magnitude in each complex from about 5 times to about one-quarter of the average value in the solar neighborhood. Within a complex, color variations are seen on all scales. No significant variations of the I(v)(100 micron)/A(v) ratio are observed between clouds of widely different mid- to far-IR color. It is shown that neither the large amplitude of the color variations nor their morphology can be explained by changes of the excitation by the UV radiation field and it is concluded that the color variations trace variations in the abundance of transiently heated particles. A scenario is proposed which relates the abundance variations to the cycling of interstellar matter between the gas-phase and grain surfaces.

Boulanger, F.↗

Detection of the 3.4 micron emission feature in Comets P/Brorsen-Metcalf and Okazaki-Levy-Rudenko (1989r) and an observational summary

The 3.4 micron emission feature due to cometary organics was detected in Comets P/Brorsen-Metcalf and Okazaki-Levy-Rudenko (1989r). Features-to-continuum ratios in these two comets were higher than those expected from the trend seen in other comets to date. Three micron spectra of eight comets are reviewed. The 3.4 micron band flux is better correlated with the water production rate than with the dust production rate in this sample of comets. High feature-to-continuum ratios in P/Brorsen-Metcalf and Okazaki-Levy-Rudenko can be explained by the low dust-to-gas ratios of these two comets. The observations to date are consistent with cometary organics being present in all comets (even those for which no 3.4 micron feature was evident) at comparable abundances with respect to water. The emission mechanism and absolute abundance of the organics are not well determined; either gas-phase fluorescence or thermal emission from hot grains is consistent with the heliocentric distance dependence of the 3.4 micron band flux. There is an overall similarity in the spectral profiles of the 3.4 micron feature in comets; however, there are some potentially significant differences in the details of the spectra.

Brooke, T. Y.↗

Ignition delay of a gas mixture above a liquid fuel pool

A computational study has been made of transient heat transfer and fluid flow of an axisymmetric two-layer gas-and-liquid system heated from above by a small hot spot (e.g., a hot wire or pilot flame) located close to the liquid surface. The gas phase is unconfined above the liquid pool. The effects of varying gravity level (0.0001 to 1 gn), liquid pool height, and heater height are investigated. Thermocapillary convection induced by the nonuniform heating of the liquid surface combines with buoyancy forces to affect the heat transfer and the transport of fuel vapor toward the heat source. At reduced gravity, gas-phase conduction is comparable to the incident radiation at the liquid surface, whereas at 1 gn, buoyant convection carries the heat upward from the heat source and, therefore, the liquid is heated primarily by radiation.

Schiller, D. N.↗

Comment on 'A non-mass-dependent isotopic fractionation effect' by F. Robert, J. Halbout and J. Baudon

The fractionation model of Robert et al. (1988) treats the gas-phase isotopic exchange reaction between kinetically excited atoms aX and diatomic MbX yielding bX and MaX and finds an abundance-dependent fractionation superimposed on the usual mass dependent fractionation. This paper shows that the treatment of Robert et al. is in error and presents a more straightforward treatment of the same system. This model shows only mass-dependent fractionation.

Sund, Mark T.↗

Thermal management of advanced fuel cell power systems

It is shown that fuel cell devices are particularly attractive for the high-efficiency, high-reliability space hardware necessary to support upcoming space missions. These low-temperature hydrogen-oxygen systems necessarily operate with two-phase water. In either PEMFCs (proton exchange membrane fuel cells) or AFCs (alkaline fuel cells), engineering design must be critically focused on both stack temperature control and on the relative humidity control necessary to sustain appropriate conductivity within the ionic conductor. Water must also be removed promptly from the hardware. Present designs for AFC space hardware accomplish thermal management through two coupled cooling loops, both driven by a heat transfer fluid, and involve a recirculation fan to remove water and heat from the stack. There appears to be a certain advantage in using product water for these purposes within PEM hardware, because in that case a single fluid can serve both to control stack temperature, operating simultaneously as a heat transfer medium and through evaporation, and to provide the gas-phase moisture levels necessary to set the ionic conductor at appropriate performance levels. Moreover, the humidification cooling process automatically follows current loads. This design may remove the necessity for recirculation gas fans, thus demonstrating the long-term reliability essential for future space power hardware.

Vanderborgh, N. E.↗

Non-isotropic turbulence effects on spray combustion

A numerical model for the prediction of local properties of statistically stationary spray-combusting flows is evaluated by comparison with experimental data. To appraise the relative performance of turbulence models, computations were carried out by the k-epsilon model and the algebraic stress model. The present numerical results show the qualitative agreement with experimental data. In terms of overall local flow properties, the algebraic stress model improves a degree of conformity to the experimental data due to its ability to introduce the nonisotropic turbulence effects. Two swirl numbers are considered to investigate the influence of swirl on the droplet evaporation and trajectories, and the effects of droplet/turbulence interactions in flow properties. It is found that the large swirl produces a higher evaporationn rate, and more intensive turbulent mixing and burning. The discrepancies observed in the results are attributed mainly to uncertainties in the initial spray size and velocity distributions, the droplet/wall impingement interaction, the combustion model with the fast chemistry and the turbulence models dealing with the strong streamline curvature and complex interactions between the dispersed droplets and the continuous gas-phase flows.

Kim, Y. M.↗

Detonability of hydrocarbon fuels in air

Studies were conducted of the detonation of gas-phase mixtures of n-hexane and JP-4, with oxidizers as varied as air and pure oxygen, measuring detonation velocities and cell sizes as a function of stoichiometry and diluent concentration. The induction length of a one-dimensional Zeldovich-von Neumann-Doering detonation was calculated on the basis of a theoretical model that employed the reaction kinetics of the hydrocarbon fuels used. Critical energy and critical tube diameter are compared for a relative measure of the heavy hydrocarbon fuels studied; detonation sensitivity appears to increase slightly with increasing carbon number.

Beeson, H. D.↗

The Effect of Gravity on the Combustion of Bulk Metals

In recent years, metal combustion studies at the University of Colorado have focused on the effects of gravity (g) on the ignition and burning behavior of bulk metals. The impetus behind this effort is the understanding of the ignition conditions and flammability properties of structural metals found in oxygen (O2) systems for space applications. Since spacecraft are subjected to higher-than-1g loads during launch and reentry and to a zero-gravity environment while in orbit, the study of ignition and combustion of bulk metals at different gravitational accelerations is of great practical concern. From the scientific standpoint, studies conducted under low gravity conditions provide simplified boundary conditions, since buoyancy is removed, and make possible the identification of fundamental ignition and combustion mechanisms. This investigation is intended to provide experimental verification of the influence of natural convection on the burning behavior of metals. In addition, the study offers the first findings of the influence of gravity on ignition of bulk metals and on the combustion mechanism and structure of metal-oxygen, vapor-phase diffusion flames in a buoyancy-free environment. Titanium (Ti) and magnesium (Mg) metals were chosen because of their importance as elements of structural materials and their simple chemical composition-pure metals instead of multicomponent alloys to simplify chemical and spectroscopic analyses. In addition, these elements present the two different combustion modes observed in metals: heterogeneous or surface burning (for Ti) and homogeneous or gas-phase reaction (for Mg). Finally, Mg, Ti, and their oxides exhibit a wide range of thermophysical and chemical properties. Metal surface temperature profiles, critical and ignition temperatures, propagation rates, burning times, and spectroscopic measurements are obtained under normal and reduced gravity. Visual evidence of all phenomena is provided by high-speed photography.

Branch, Melvyn C.↗

Effect of Surface Preparation and Gas Flow on Nitrogen Atom Surface Recombination

The effects of surface preparation and gas flow on the recombination of nitrogen atoms at copper and platinum surfaces were determined. Atoms were generated by an electrodeless 2450-megacycle-per-second discharge, and their concentration was measured by gas-phase titration with nitric oxide. Test surfaces were either vacuum-evaporated films or spheres machined from bulk metal and cemented around small glass-bead thermistors. Heat released by recombination was measured as the difference in electrical energy required to maintain a given thermistor temperature with and without a catalytic surface exposed. Recombination coefficients measured at flow velocities of 1120, 1790, 2250, and 3460 centimeters per second and at pressures of 0.42 and 0.59 millimeter of mercury showed that flow conditions had no effect. The results were also independent of atom concentration. A rough indication of the temperature dependence was obtained; it was greater for copper than for platinum. Platinum films deposited on platinum or on glass had the same activity - about 3 percent of the atoms impinging recombined. With copper, however, the glass substrate greatly reduced the percent of atoms recombining over that of a bulk copper substrate where 4 percent of the impinging atoms recombined. This effect could be overcome by depositing a second film on top of the first. Bulk metal samples were subjected to various surface treatments including polishing, degreasing with a chlorinated hydrocarbon, washing with nitric acid, and rinsing with water. Polished, degreased platinum had low activity compared to an evaporated film, but nitric acid treatment made it equivalent. Polished, degreased copper was only slightly less active than a copper film; nitric acid etching decreased the activity still further, probably by preferentially exposing facets of low catalytic efficiency.

Prok, George M.↗