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Interstellar H2S has been detected toward the cold, dark clouds L134N and TMC 1. Total column densities at the SO peak of L134N and the NH3 peak of TMC 1 are found to be about 2.6 X 10 to the 13th/sq cm and 7.0 X 10 to the 12th/sq cm, respectively. The results suggest that grain surface reactions may play a major role in the synthesis of H2S in cold, dark clouds.
Synchrotron-radiation sources and their characteristics are overviewed along with recent synchrotron-based research on earth materials and future earth-science applications utilizing the next generation of synchrotron-radiation sources presently under construction. Focus is placed on X-ray scattering studies of earth materials (crystalline and noncrystalline) under ambient conditions, diffraction studies of earth materials at high pressures and/or temperatures, spectroscopic studies, primarily X-ray absorption spectroscopy, and spatially resolved X-ray fluorescence studies of compositional variations in earth materials. It is noted that other synchrotron-based methods, such as X-ray tomography and topography may become important in characterizing earth materials, while soft X-ray/vacuum ultraviolet radiation from synchrotron sources can be applied to problems involving the structural environments of low-atomic-number elements and the characterization of surface reactions of minerals with liquids and gases.
A recently detected absorption feature at 3.53 microns in the spectrum of W33A has been assigned to methanol (CH3OH). Its optical depth implies that methanol is the second most abundant molecule (7 percent relative to H2O) in the grain mantles in the line of sight toward W33A observed to date. Laboratory experiments have shown that the implied abundance is difficult to explain by UV irradiation of the dust grains alone. Grain surface reactions or condensation directly out of the gas phase must also play roles, but the relative contributions of the various processes are difficult to estimate. The optical depth of the 3.53-micron feature constrains the contribution of methanol to the 6.8-micron feature in W33A to be 10 percent or less, requiring the contribution of at least one other compound to this feature, while the estimated contribution to the 4.9-micron absorption band is even smaller. Only a small contribution of formaldehyde (H2CO) is consistent with the observed 3.53-micron band profile. In contrast to methanol, formaldehyde can be produced readily by photochemical reactions within the ice mantle.
A feasibility study assessing the utility of the adaptation of near infrared correlation spectroscopy to quantifying iron and adsorbed water in some clay-based Mars soil analog materials (MarSAM's). The work was intended to constitute Phase 1 of an approach to identifying optical analytical wavelength regions, not only for important mineral classes, but for chemically active centers within them. Many of these centers are common to unrelated mineral classes and of disproportionate influence relative to the mineral structure as a whole in determining the surface reactivity of mineral surfaces. We previously reported linearity between reflectance and total iron and total moisture over a large range of both key variables. We also discovered interesting relationships between the intensity of iron bands and the relative humidity of the systems. These relationships were confirmed. We also show that, in the low humidity range, reflectance is linearly dependent on a different kind of water from that best representing the full humidity range (the kind of water associated, in clays, with surface acidity). These relationships and the sensitivity and capability of quantitation of near infrared data indicate high promise with the production of reactive surface intermediates of products of surface reactions.
A knowledge of the original volatile endowment of Mars is essential for any discussion of atmospheric loss on this planet. Cosmochemical models which postulate that planetary bulk compositions and volatile contents were controlled by the radial temperature profile in the solar nebula, and estimated bulk compositions based on the assumption that Mars is the parent body for the SNC meteorites predicts that Mars is volatile-rich. However, contrary views can also be found. For illustrative purposes, it is assumed that Mars was volatile-rich initially like the Earth. Taking terrestrial volatiles as the sum of the atmospheric, crustal, and oceanic volatiles and assuming that Mars accreted with the same volatile content on a g/g basis, the volatile endowments for an Earth-like Mars correspond to approximately 14 bars CO2, 800 mbars N2, and 1.2 km H2O. Subsequent topics discussed are: composition of outgassing volatiles; rates of present day atmospheric-surface reactions; constraints on CO2 loss via carbonate formation; constraints on H2O loss; and loss of other volatiles.
This paper describes an analytical model of an incompressible, isothermal reacting jet in crossflow. The model represents the flow in the jet cross-section by a counter rotating vortex pair, a flow structure that has been observed to dominate the jet behavior. The reaction surface surrounding the fuel jet is represented as a composite of strained diffusion flames that are stretched and deformed by the vortex pair flow. The results shed new light on the interaction between the vortex pair circulation and flame structure evolution and their relation to the concept of entrainment.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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).