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At least 217 records · Page 12

The permanent electric dipole moment of chromium monoxide

The permanent electric dipole moments for the X 5Pi and B 5pi states of gas-phase CrO have been experimentally determined using the sub-Doppler optical technique of intermodulated fluorescence spectroscopy in conjunction with the Stark effect. The measured values are 3.88 + or - 0.13 and 4.1 + or - 1.8 D for the X and B states, respectively. The theoretical values determined for the X state using multireference CI iterative-natural-orbital and finite-field calculations are in excellent agreement with the experimental value.

Steimle, Timothy C.↗

The effect of hydrogen and microstructure on the deformation and fracture behavior of a single crystal nickel-base superalloy

A study was conducted on the effects of internal hydrogen and microstructure on the deformation and fracture of a single crystal nickel-base superalloy. In particular, room temperature plane strain fracture toughness and tensile tests were performed on hydrogen-free and hydrogen charged samples of PWA 1480. The role of microstructure was incorporated by varying the levels of porosity and eutectic gamma/gamma prime through hot isostatic pressing and heat treatment. The room temperature behavior of PWA 1480 was unusual because precipitate shearing was not the primary deformation mechanism at all strains. At strains over 1 percent, dislocations were trapped in the gamma matrix and an attempt was made to relate this behavior to compositional differences between PWA 1480 and other superalloys. Another unique feature of the tensile behavior was cleavage of the eutectic gamma/gamma prime, which is believed to initiate the failure process. Fracture occurred on (111) planes and is likely a result of shear localization along these planes. Elimination of the eutectic gamma/gamma prime greatly improved the tensile ductility, but pososity had no effect on tensile properties. Large quantities of hydrogen (1.74 at. percent) were gas-phase charged into the material, but surprisingly this was not a function of the amount of porosity or eutectic gamma/gamma prime present. Desorption experiments suggest that the vast majority of hydrogen is at reversible lattice trapping sites. This large, uniform concentration of hydrogen dramatically reduced the tensile strain to failure, but only slightly affected the reduction in area. Available hydrogen embrittlement models were examined in light of these results and it was found that the hydrogen enhanced localized plasticity model can explain much of the tensile behavior. K(IC) fracture toughness tests were conducted, but it was necessary to also perform J(IC) tests to provide valid data.

Walston, William S.↗

Laboratory investigations: Low Earth orbit environment chemistry with spacecraft surfaces

Long-term space operations that require exposure of material to the low earth orbit (LEO) environment must take into account the effects of this highly oxidative atmosphere on material properties and the possible contamination of the spacecraft surroundings. Ground-based laboratory experiments at Los Alamos using a newly developed hyperthermal atomic oxygen (AO) source have shown that not only are hydrocarbon based materials effected but that inorganic materials such as MoS2 are also oxidized and that thin protective coatings such as Al2O3 can be breached, producing oxidation of the underlying substrate material. Gas-phase reaction products, such as SO2 from oxidation of MoS2 and CO and CO2 from hydrocarbon materials, have been detected and have consequences in terms of spacecraft contamination. Energy loss through gas-surface collisions causing spacecraft drag has been measured for a few select surfaces and has been found to be highly dependent on the surface reactivity.

Cross, Jon B.↗

Rate of formation of the ClO dimer in the polar stratosphere - Implications for ozone loss

The gas-phase recombination of chlorine monoxide (ClO) has been investigated under the conditions of pressure and temperature that prevail in the Antarctic stratosphere during the period of maximum ozone (O3) disappearance. Measured rate constants are less than one-half as great as the previously accepted values. One-dimensional model calculations based on the new rate data indicate that currently accepted chemical mechanisms can quantitatively account for the observed O3 losses in late spring (17 September to 7 October). A qualitative assessment indicates that the existing mechanisms can only account for at most one-half of the measured O3 depletion in the early spring (28 August to 17 September), indicating that there may be additional catalytic cycles, besides those currently recognized, that destroy O3.

Sander, Stanley P.↗

Diffuse cloud chemistry

The current status of models of diffuse interstellar clouds is reviewed. A detailed comparison of recent gas-phase steady-state models shows that both the physical conditions and the molecular abundances in diffuse clouds are still not fully understood. Alternative mechanisms are discussed and observational tests which may discriminate between the various models are suggested. Recent developments regarding the velocity structure of diffuse clouds are mentioned. Similarities and differences between the chemistries in diffuse clouds and those in translucent and high latitude clouds are pointed out.

Van Dishoeck, Ewine F.↗

The 2175-A feature from irradiated graphitic particles

In diffuse clouds, a subpopulation of the carbon grains is graphitized by UV starlight during cloud lifetimes of roughly 100 Myr. Graphitic dust created in this way will behave like monosize Rayleigh particles and produce a 2175-A absorption band showing a Lorentzian profile. A physical model is outlined in which the strength and width of the band correlate with the dust grain environment, but the central wavelength is fixed by the Froehlich frequency for surface plasmons in a homogeneous sphere. On this model, the band appears strong and narrow only in dust clouds where the flux of UV starlight is high and the H atom gas density is low. The width of the band increases from diffuse to dense clouds mainly as a result of gas-phase H atoms accreted on to the grain surface. It is shown that hydrogenation weakens the band in dense clouds, and thus explains the anticorrelation between band strength and high carbon depletion. The model as a whole uses only 30 percent of the cosmic carbon and gives good agreement with observations of the 2175-A feature and the average interstellar extinction law.

Sorrell, Wilfred H.↗

Opposed-flow flame spread and extinction in mixed-convection boundary layers

Experimental data for flame spread down thin fuel samples in an opposing, mixed-convection, boundary-layer flow are analyzed to determine the gas-phase velocity that characterizes how the flame reacts as it spreads toward the leading edge of the fuel sample into a thinning boundary layer. In the forced-flow limit where the cube of the Reynolds number divided by the Grashof number, Re exp 3/Gr, is large, L(q)/L(e), where L(q) is a theoretical flame standoff distance at extinction and L(e) is the measured distance from the leading edge of the sample where extinction occurs, is found to be proportional to Re exp n with n = -0.874 and Re based on L(e). The value of n is established by the character of the flow field near the leading edge of the flame. The Re dependence is used, along with a correction for the mixed-convection situation where Re exp 3/Gr is not large, to construct a Damkohler number with which the measured spread rates correlate for all values of Re exp 3/Gr.

Altenkirch, R. A.↗

ISM-induced erosion and gas-dynamical drag in the Oort Cloud

The model presently used to examine the physical interactions between the ISM and the Oort Cloud can account for sputtering, sticking, and grain-impact erosion, as well as gas drag, by envisioning the ISM as a multiphase medium with distinct atomic and molecular cloud-phase regimes and coronal and warm/ambient gas-phase regimes. Erosion, which reduces the effectiveness of the thermal and radiation-damage processes acting on cometary surfaces in the Oort cloud, is found to be the dominant ISM interaction; ISM drag effects were found to efficiently remove submicron particles from the Cloud.

Stern, S. Alan↗

Model simulations of rainout and washout from a warm stratiform cloud

A one-dimensional, time-dependent cloud model with parameterized microphysics is used to investigate the processes which control the rainout and washout of soluble gases from warm, precipitating stratiform clouds. Calculations are presented simulating the distributions of soluble species within and below the cloud layer and in the precipitating raindrops as a function of time and species' solubility. Calculations indicate that for species with low solubility, wet removal processes are relatively slow and thus do not significantly affect the species' gas-phase abundance. As a result, the removal of low-solubility species by rainout and washout is controlled by thermodynamic processes with the concentration of the species in cloud and rainwater largely determined by the species' solubility. For highly soluble species on the other hand, dissolution into cloud droplets and removal in rain is quite rapid and the abundance of highly soluble species within and below the cloud falls rapidly as soon as the precipitation begins.

Xing, Lin↗

Dissociative recombination in interstellar clouds

Molecular ions play a significant role in the chemistry and evolution of interstellar molecular clouds, even though these regions are overwhelmingly neutral. The dissociative recombination (DR) process governs the abundances of many of these ions and of related neutral species. The gas-phase ion-molecule chemistry of the simplest species is summarized, with emphasis on those problems which are most sensitive to uncertain rates or product branching ratios of DR processes. Examples of the kinds of information needed about DR processes are presented. The importance of the H3(+) ion and prospects for its direct observation are discussed.

Black, John H.↗

LOX vaporization in high-pressure, hydrogen-rich gas

LOX droplet vaporization in high-pressure hydrogen-rich gas is analyzed, with special attention to thermodynamic effects which compel the surface to heat to the critical state and to supercritical vaporization processes on heating to criticality. Subcritical vaporization is modeled using a quasi-steady diffusion-controlled gas-phase transport formulation coupled to an effective-conductivity internal-energy-transport model accounting for circulation effects. It is demonstrated how the droplet surface might heat to the critical state, for ambient pressures slightly greater than the critical pressure of oxygen, such that the bulk of propellant within the droplet remains substantially below the critical mixing temperature.

Litchford, Ron J.↗

Hypergolic bipropellant spray combustion and flow modelling in rocket engines

A predictive tool for hypergolic bipropellant spray combustion and flow evolution in small rocket combustion chambers is described. It encompasses a computational technique for the gas-phase governing equations, a discrete particle method for liquid bipropellant sprays, and constitutive models for combustion chemistry, interphase exchanges, and unlike impinging hypergolic spray interactions. Emphasis is placed on the phenomenological modeling of the hypergolic liquid bipropellant gasification processes. Sample computations with the N2H4-N2O4 propellant system are given in order to show some of the capabilities and inadequacies of this tool.

Larosiliere, Louis M.↗

Ultraviolet gas absorption and dust extinction toward M8

Interstellar absorption lines are analyzed using high-resolution IUE spectra of 11 stars in the young cluster NGC 6530 located in the M8 region. High-velocity clouds at -35 km/s and -60 km/s are seen toward all cluster stars. The components arise in gases that are part of large interstellar bubbles centered on the cluster and driven by stellar winds of the most luminous members. Absorption lines of species of different ionization states are separated in velocity. The velocity stratification is best explained as a 'champagne' flow of ionized gas away from the cluster. The C IV/Si IV ratios toward the hotter cluster members are consistent with simple photoionization models if the gas-phase C/Si ratio is increased by preferential accretion onto dust grains. High ion column densities in the central cluster decline with distance from W93, suggesting that radiation from a hot source near W93 has photoionized gas in the central cluster.

Boggs, Don↗

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.↗

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↗