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At least 163 records · Page 9

On the weathering of Martian igneous rocks

Besides the young crystallization age, one of the first arguments for the martian origin of shergottite, nakhlite, and chassignite (SNC) meteorites came from the chemical similarity of the meteorite Shergotty and the martian soil as measured by Viking XRF analyses. In the meantime, the discovery of trapped rare gas and nitrogen components with element and isotope ratios closely matching the highly characteristic ratios of the Mars atmosphere in the shock glasses of shergottite EETA79001 was further striking evidence that the SNC's are martian surface rocks. The martian soil composition as derived from the Viking mission, with its extremely high S and Cl concentrations, was interpreted as weathering products of mafic igneous rocks. The low SiO2 content and the low abundance of K and other trace elements in the martian soils point to a mafic crust with a considerably smaller degree of fractionation compared to the terrestrial crust. However, the chemical evolution of the martian regolith and soil in respect to surface reaction with the planetary atmosphere or hydrosphere is poorly understood. A critical point in this respect is that the geochemical evidence as derived from the SNC meteorites suggests that Mars is a very dry planet that should have lost almost all its initially large water inventory during its accretion.

Dreibus, G.↗

A semi-empirical model for the complete orientation dependence of the growth rate for vapor phase epitaxy - Chloride VPE of GaAs

A semi-empirical model has been developed to determine the complete crystallographic orientation dependence of the growth rate for vapor phase epitaxy (VPE). Previous researchers have been able to determine this dependence for a limited range of orientations; however, our model yields relative growth rate information for any orientation. This model for diamond and zincblende structure materials is based on experimental growth rate data, gas phase diffusion, and surface reactions. Data for GaAs chloride VPE is used to illustrate the model. The resulting growth rate polar diagrams are used in conjunction with Wulff constructions to simulate epitaxial layer shapes as grown on patterned substrates. In general, this model can be applied to a variety of materials and vapor phase epitaxy systems.

Seidel-Salinas, L. K.↗

Growth kinetics and characterizations of gallium nitride thin films by remote PECVD

Thin films of GaN have been deposited at relatively low growth temperatures by remote plasma-enhanced chemical-vapor deposition (RPECVD), using a plasma excited NH3, and trimethylgallium (TMG), injected downstream from the plasma. The activation energy for GaN growth has been tentatively assigned to the dissociation of NH groups as the primary N-atom precursors in the surface reaction with adsorbed TMG, or TMG fragments. At high He flow rates, an abrupt increase in the growth rate is observed and corresponds to a change in the reaction mechanism attributed to the formation of atomic N. XRD reveals an increased tendency to ordered growth in the (0001) direction with increasing growth temperature, He flow rate, and RF plasma power. IR spectra show the fundamental lattice mode of GaN at 530 cm without evidence for vibrational modes of hydrocarbon groups.

Choi, S. W.↗

Computer modeling of a hot filament diamond deposition reactor

A commercial fluid mechanics program, FLUENT, has been applied to the modeling of a hot-filament diamond deposition reactor. Streamlines and contours of constant temperature and species concentrations are obtained for practical reactor geometries and conditions. The modeling is presently restricted to two-dimensional simulations and to a chemical mechanism of ten independent homogeneous and surface reactions. Comparisons are made between predicted power consumption, substrate temperature, and concentrations of atomic hydrogen and methyl-radical with values taken from the literature. The results to date indicate that the modeling can aid in the rational design and analysis of practical reactor configurations.

Kuczmarski, Maria A.↗

In situ measurements constraining the role of sulphate aerosols in mid-latitude ozone depletion

In situ measurements of stratospheric sulphate aerosol, reactive nitrogen and chlorine concentrations at middle latitudes confirm the importance of aerosol surface reactions that convert active nitrogen to a less active, reservoir form. This makes mid-latitude stratospheric ozone less vulnerable to active nitrogen and more vulnerable to chlorine species. The effect of aerosol reactions on active nitrogen depends on gas phase reaction rates, so that increases in aerosol concentration following volcanic eruptions will have only a limited effect on ozone depletion at these latitudes.

Fahey, D. W.↗

Nucleation and growth of crystals under cirrus and polar stratospheric cloud conditions

Laboratory studies examine phase changes of hygroscopic substances which occur as aerosol in stratosphere and troposphere (sodium chloride, ammonium sulfate, ammonium bisulfate, nitric acid, sulfuric acid), under controlled conditions, in samples volume 1 to 10(exp -4) ml. Crystallization of salts from supersaturated solutions is examined by slowly evaporating a solution drop on a substrate, under controlled relative humidity, until self nucleation occurs; controlled nucleation of ice in a mm capillary U-tube gives a measured ice crystallization velocity at known supercooling. Two states of crystallization occur for regions where hydrates exist. It is inferred that all of the materials readily exist as supersaturated/supercooled solutions; the degree of metastability appears to be slightly enhanced by inclusion of aircraft produced soot. The crystallization velocity is taken as a measure of viscosity. Results suggest an approach to a glass transition at high molality, supersaturation and/or supercooling within the range of atmospheric interest. It is hypothesized that surface reactions occur more readily on solidified particles - either crystalline or glass, whereas volume reactions are more important on droplets with sufficiently low viscosity and volume diffusivity. Implications are examined for optical properties of such particles in the atmosphere. In a separate experiment, crystal growth was examined in a modified thermal vapor diffusion chamber over the range of cirrus temperature (-30 to -70 C) and under controlled supersaturation and air pressure. The crystals grew at a velocity of 1-2 microns/s, thickness 60-70 micron, in the form of thin column crystals. Design criteria are given for a system to investigate particle growth down to -100 C, (PSC temperatures) where nitric acid particles can be grown under similar control and in the form of hydrate crystals.

Hallett, John↗

STS-46 plasma composition measurements using the EOIM-3 mass spectrometer

One of the active instruments incorporated into the Evaluation of Oxygen Interactions with Materials - 3 experiment was a quadrupole mass spectrometer. The primary objectives for this instrument, which was built by the Air Force Phillips Laboratory and was a veteran of the STS-4 flight in 1982, were to quantify the flux of atomic oxygen striking the test surfaces in the EOIM-3 payload and to detect surface reaction products from the materials in the carousel. Other speakers in this session have covered the results of these experiments. Prior to the 40-hour-long dedicated EOIM-3 mission segment at the end of the STS-46 flight, the authors used the mass spectrometer to make measurements of ion and neutral gas composition in the shuttle environment. About 25 hours of data were collected during a variety of mission events, including Eureca deployment at high altitude and many tethered satellite system operations.

Hunton, Donald E.↗

Internal and surface phenomena in metal combustion

Combustion of metals has been widely studied in the past, primarily because of their high oxidation enthalpies. A general understanding of metal combustion has been developed based on the recognition of the existence of both vapor-phase and surface reactions and involvement of the reaction products in the ensuing heterogeneous combustion. However, distinct features often observed in metal particle combustion, such as brightness oscillations and jumps (spearpoints), disruptive burning, and non-symmetric flames are not currently understood. Recent metal combustion experiments using uniform high-temperature metal droplets produced by a novel micro-arc technique have indicated that oxygen dissolves in the interior of burning particles of certain metals and that the subsequent transformations of the metal-oxygen solutions into stoichiometric oxides are accompanied with sufficient heat release to cause observed brightness and temperature jumps. Similar oxygen dissolution has been observed in recent experiments on bulk iron combustion but has not been associated with such dramatic effects. This research addresses heterogeneous metal droplet combustion, specifically focusing on oxygen penetration into the burning metal droplets, and its influence on the metal combustion rate, temperature history, and disruptive burning. A unique feature of the experimental approach is the combination of the microgravity environment with a novel micro-arc Generator of Monodispersed Metal Droplets (GEMMED), ensuring repeatable formation and ignition of uniform metal droplets with controllable initial temperature and velocity. The droplet initial temperatures can be adjusted within a wide range from just above the metal melting point, which provides means to ignite droplets instantly upon entering an oxygen containing environment. Initial droplet velocity will be set equal to zero allowing one to organize metal combustion microgravity experiments in a fashion similar to usual microgravity liquid fuel droplet combustion studies. In addition, the internal compositions of rapidly quenched metal particles will be analyzed using SEM technique. Such compositions are similar to those existing during the combustion and provide new insight on metal combustion processes. The results of this experimental work will be used to model the fundamental mechanisms of metal combustion. Preliminary experimental results on Al and Zr particle combustion at normal gravity are discussed here.

Dreizin, Edward L.↗

Deuterated Water in Comet C/1996 B2 (Hyakutake) and its Implications for the Origin of Comets

The close approach to the Earth of comet C/1996 B2 (Hyakutake) in March 1996 allowed searches for minor volatile species outgassing from the nucleus. We report the detection of deuterated water (HDO) through its 1(sub 01)-0(sub 00) rotational transition at 464.925 GHz using the Caltech Submillimeter Observatory. We also present negative results of a sensitive research for the J(5-4) line of deuterated hydrogen cyanide (DCN) at 362.046 GHz. Simultaneous observations of two rotational lines of methanol together with HDO in the same spectrum allow us to determine the average gas temperature within the telescope beam to be 69 +/- 10 K. We are thus able to constrain the excitation conditions in the inner coma and determine reliably the HDO production rate as (1.20 +/- 0.28) x 10(exp 26)/s on March 23-24, 1996. Available IR, UV and radio measurements lead to a water production rate of (2.1 +/- 0.5) x 10(exp 29)/s at the time of our HDO observations. The resulting D/H ratio in cometary water is thus (29 +/- 10) x 10(exp -5) in good agreement with the values of (30.8(sub - 5.3, sup +3.8) (Balsiger et al. 1995) and (31.6 +/- 3.4) x 10(exp -5) (Eberhardt et al. 1995) determined in comet P/Halley from in situ ion mass spectra. The inferred 3 a upper limit for the D/H ratio in HCN is 1%. Deuterium abundance is a key parameter for studying the origin and the early evolution of the Solar System and of its individual bodies. Our HDO measurement confirms that, in cometary water, deuterium is enriched by a factor of at least 10 relative to the protosolar ratio, namely the D/H ratio in H2 in the primitive Solar Nebula which formed from the collapse of the protosolar cloud. This indicates that cometary water has preserved a major part of the high D/H ratio acquired in this protosolar cloud through ion-molecule isotopic exchanges or grain-surface reactions and was not re-equilibrated with H2 in the Solar Nebula. Scenarios of formation of comets consistent with these results are discussed.

Bockelee-Morvan, D.↗

Oxidative Attack of Carbon/Carbon Substrates through Coating Pinholes

A critical issue with oxidation protected carbon/carbon composites used for spacecraft thermal protection is the formation of coating pinholes. In laboratory experiments, artificial pinholes were drilled through SiC-coatings on a carbon/carbon material and the material was oxidized at 600, 1000, and 1400 C at reduced pressures of air. The attack of the carbon/carbon was quantified by both weight loss and a novel cross-sectioning technique. A two-zone, one dimensional diffusion control model was adapted to analyze this problem. Agreement of the model with experiment was reasonable at 1000 and 1400 C; however results at lower temperatures show clear deviations from the theory suggesting that surface reaction control plays a role.

Jacobson, Nathan S.↗

Interstellar Ice and Dust: The Feedstock of the Solar System

Studying the chemical and isotopic composition of interstellar ice and dust provides insight into the composition and chemical history of the solid bodies in the solar nebula and the nature of the material subsequently brought into the inner part of the solar system by comets and meteorites. It is now possible to probe the composition of these microscopic interstellar particles (some hundreds of light years away), thanks to substantial progress in two areas: astronomical spectroscopic techniques in the middle-infrared, the spectral region most diagnostic of composition; and laboratory simulations which realistically reproduce the critical conditions in various interstellar environments. High quality infrared spectra of many different astronomical sources, some associated with dark molecular clouds, and others in the diffuse interstellar medium (DISM) are now available. What comparisons of these spectra with laboratory spectra tell us about the complex organic components of these materials is the subject of this talk. Most interstellar material is concentrated in large molecular clouds where simple molecules are formed by gas phase and dust grain surface reactions. Gaseous species (except H2) striking the cold (10K) dust will stick, forming an icy grain mantle. This accretion, coupled with energetic particle bombardment and UV photolysis, will produce a complex chemical mixture containing volatile, non-volatile, and isotopically fractionated species. One can compare spectra of the diffuse and dense interstellar medium with the spectra of analogs produced in the laboratory under conditions which mimic those in these different environments. In this way one can determine the composition and abundances of the major constituents present and place general constraints on the types and relative abundances of organics coating the grains. Ices in dense clouds contain H2O, CH3OH, CO, perhaps some NH3 and H2CO, as well as nitriles and ketones or esters. There is some evidence that the later, more complex species, are also present on the grains in the DISM. The evidence for these materials, in addition to carbon rich materials such as amorphous carbon, microdiamonds, and polycyclic aromatic hydrocarbons will be reviewed and the possible connection with meteoritic organics will be discussed.

Allamandola, L. J.↗

General Model for Multicomponent Ablation Thermochemistry

A previous paper (AIAA 94-2042) presented equations and numerical procedures for modeling the thermochemical ablation and pyrolysis of thermal protection materials which contain multiple surface species. This work describes modifications and enhancements to the Multicomponent Ablation Thermochemistry (MAT) theory and code for application to the general case which includes surface area constraints, rate limited surface reactions, and non-thermochemical mass loss (failure). Detailed results and comparisons with data are presented for the Shuttle Orbiter reinforced carbon-carbon oxidation protection system which contains a mixture of sodium silicate (Na2SiO3), silica (SiO2), silicon carbide (SiC), and carbon (C).

Milos, Frank S.↗

Astronomical Problems and Laboratory Solutions

Studying the chemical and isotopic composition of interstellar ice and dust provides insight into the composition and chemical history of the solid bodies in the solar nebula and the nature of the material subsequently brought into the inner part of the solar system by comets and meteorites. It is now possible to probe the composition of these microscopic interstellar particles (some hundreds of light years away), thanks to substantial progress in two areas: astronomical spectroscopic techniques in the middle-infrared, the spectral region most diagnostic of composition; and laboratory simulations which realistically reproduce the critical conditions in various interstellar environments. High quality infrared spectra of many different astronomical sources, some associated with dark molecular clouds, and others in the diffuse interstellar medium (DISM) are now available. What comparisons of these spectra with laboratory spectra tell us about the complex organic components of these materials is the subject of this talk. Most interstellar material is concentrated in large molecular clouds where simple molecules are formed by gas phase and dust grain surface reactions. Gaseous species (except H2) striking the cold (10K) dust will stick, forming an icy grain mantle. This accretion, coupled with energetic particle bombardment and UV photolysis, will produce a complex chemical mixture containing volatile, non-volatile, and isotopically fractionated species. One can compare spectra of the diffuse and dense interstellar medium with the spectra of analogs produced in the laboratory under conditions which mimic those in these different environments. In this way one can determine the composition and abundances of the major constituents present and place general constraints on the types and relative abundances of organics coating the grains. Ices in dense clouds contain H2O, CH3OH, CO, perhaps some NH3 and H2CO, as well as nitriles and ketones or esters. there is some evidence that the later, more complex species, are also present on the grains in the DISM. The evidence for these materials, in addition to carbon rich materials such as amorphous carbon, microdiamonds, and polycyclic aromatic hydrocarbons will be reviewed and the possible connection with meteoritic organics will be discussed.

Allamandola, L. J.↗

Oxidation Behavior of HfB2-SiC Materials in Dissociated Environments

Hafnium diboride based materials have shown promise for use in extremely high temperature applications, such as sharp leading edges on future reentry vehicles. During reentry, the oxygen and nitrogen in the atmosphere are dissociated by the shock layer ahead of the sharp leading edge such that surface reactions are determined by reactions of monatomic oxygen and nitrogen rather than O2, and N2. Simulation of the reentry environment on the ground requires the use of arc jet (plasma jet) facilities that provide monatomic species and are the closest approximation to actual flight conditions. Simple static or flowing oxidation studies under ambient pressures and atmospheres are not adequate to develop an understanding of a materials behavior in flight. Arc jet testing is required to provide the appropriate stagnation pressures, heat fluxes, enthalpies, heat loads and atmospheres encountered during flight. This work looks at the response of HfB2/SiC materials exposed to various simulated reentry environments.

Ellerby, Don↗

Comparison of automated pre-column and post-column analysis of amino acid oligomers

It has been shown that various amino acids will polymerize under plausible prebiotic conditions on mineral surfaces, such as clays and soluble salts, to form varying amounts of oligomers (n = 2-6). The investigations of these surface reactions required a quantitative method for the separation and detection of these amino acid oligomers at the picomole level in the presence of nanomole levels of the parent amino acid. In initial high-performance liquid chromatography (HPLC) studies using a classical postcolumn o-phthalaldehyde (OPA) derivatization ion-exchange HPLC procedure with fluorescence detection, problems encountered included lengthy analysis time, inadequate separation and large relative differences in sensitivity for the separated species, expressed as a variable fluorescent yield, which contributed to poor quantitation. We have compared a simple, automated, pre-column OPA derivatization and reversed-phase HPLC method with the classical post-column OPA derivatization and ion-exchange HPLC procedure. A comparison of UV and fluorescent detection of the amino acid oligomers is also presented. The conclusion reached is that the pre-column OPA derivatization, reversed-phase HPLC and UV detection produces enhanced separation, improved sensitivity and faster analysis than post-column OPA derivatization, ion-exchange HPLC and fluorescence detection.

NASA Discipline Exobiology↗

Infrared emission spectra of candidate interstellar aromatic molecules

Interstellar dust is responsible, through surface reactions, for the creation of molecular hydrogen, the main component of the interstellar clouds in which new stars form. Intermediate between small, gas-phase molecules and dust are the polycyclic aromatic hydrocarbons (PAHs). Such molecules could account for 2-30% of the carbon in the Galaxy, and may provide nucleation sites for the formation of carbonaceous dust. Although PAHs have been proposed as the sources of the unidentified infrared emission bands that are observed in the spectra of a variety of interstellar sources, the emission characteristics of such molecules are still poorly understood. Here we report laboratory emission spectra of several representative PAHs, obtained in conditions approximating those of the interstellar medium, and measured over the entire spectral region spanned by the unidentified infrared bands. We find that neutral PAHs of small and moderate size can at best make only a minor contribution to these emission bands. Cations of these molecules, as well as much larger PAHs and their cations, remain viable candidates for the sources of these bands.

Non-NASA Center↗

Method for fabricating carbon/lithium-ion electrode for rechargeable lithium cell

The method includes steps for forming a carbon electrode composed of graphitic carbon particles adhered by an ethylene propylene diene monomer binder. An effective binder composition is disclosed for achieving a carbon electrode capable of subsequent intercalation by lithium ions. The method also includes steps for reacting the carbon electrode with lithium ions to incorporate lithium ions into graphitic carbon particles of the electrode. An electrical current is repeatedly applied to the carbon electrode to initially cause a surface reaction between the lithium ions and to the carbon and subsequently cause intercalation of the lithium ions into crystalline layers of the graphitic carbon particles. With repeated application of the electrical current, intercalation is achieved to near a theoretical maximum. Two differing multi-stage intercalation processes are disclosed. In the first, a fixed current is reapplied. In the second, a high current is initially applied, followed by a single subsequent lower current stage. Resulting carbon/lithium-ion electrodes are well suited for use as an anode in a reversible, ambient temperature, lithium cell.

Huang, Chen-Kuo↗

The Ice Line in Pre-Solar Protoplanetary Disks

Protoplanetary disks contain abundant quantities of water molecules in both gas and solid phases. The distribution of these two phases in an evolving protoplanetary disk will have important consequences regarding water sequestration in planetary embryos. The boundary between gaseous and solid water is the "ice line" or "snow line" A simplified model that captures the complicated two-branched structure of the ice line is developed and compared with recent investigations. The effect of an evolving Sun is also included for the first time. This latter parameter could have important consequences regarding the thermodynamic state and the surface reaction environment for the time-dependent chemical reactions occurring during the 1- to 10-million-year lifetime of the pre-solar disk.

Davis, Sanford S.↗