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At least 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
NASA NTRS2002

Emergence of RNA and Early Life; Experimental Modeling and Geochemical Constraints

Support from this grant continues to fund our research on two related problems. One involves attempts to model the abiotic formation of simple source compounds for functional biomolecules, their concentration from dilute state in the hydrosphere and in several cases surface induced reactions to form precursor monomers for bioactive end products. The second area is a search for the earliest traces of life on Earth and the early environments on Earth and Mars. For this purpose we have analyzed the isotopic compositions of carbon and nitrogen in graphitic residues that have been thought to represent the remains of microorganisms. The results of these studies have been presented in a number of publication, listed as references.

Arrhenius, Gustaf↗
NASA NTRS2002

Measurements of Optically Transparent and Mirrored Specimens from the POSA and EOIM III Space Flight Experiments

A selected set of optically transparent specimens and first surface mirror specimens have been examined subsequent to on-orbit exposure. Certain specimens were from the Passive Optical Sample Assembly I and II experiments flown on the MIR Space Station. Other specimens were from the Energetic Oxygen Interaction with materials III experiment flown on the STS in August 1992. A comparison of pre- and post-flight transmission of reflectance measurements, as appropriate, has been carried out. Data from different specimens includes results of measurements for IR, optical, UV and/or vacuum UV wavelength intervals. Results of these measurements clearly show the effects of molecular contamination deposits on the surfaces during the on-orbit exposures. Surface analysis on a attracted set of specimens provides and estimate of contaminant thickness and composition and provides an insight into on-orbit deposition rates and surface oxidation reactions. For both the EOIM III and POSA I & II experiments, the primary source of contamination were outgassed silicones. Both experiments received approximately the same fluence of atomic oxygen (approx. 1-2 x 1020 atoms per square centimeter). ROSA specimens received between approx. 400 and 580 equivalent sun hours (ESH) of solar radiation over an 18 month period in orbit. The EOIM specimens were on an STS flight of about 1 week duration and received only approx. 5-10 ESH of solar radiation.

Pippin, Gary↗
NASA NTRS2012

Fischer-Tropsch Cobalt Catalyst Improvements with the Presence of TiO2, La2O3, and ZrO2 on an Alumina Support

The objective of this study was to evaluate the effect of titanium oxide, lanthanum oxide, and zirconium oxide on alumina supported cobalt catalysts. The hypothesis was that the presence of lanthanum oxide, titanium oxide, and zirconium oxide would reduce the interaction between cobalt and the alumina support. This was of interest because an optimized weakened interaction could lead to the most advantageous cobalt dispersion, particle size, and reducibility. The presence of these oxides on the support were investigated using a wide range of characterization techniques such as SEM, nitrogen adsorption, x-ray diffraction (XRD), temperature programmed reduction (TPR), temperature programmed reduction after reduction (TPR-AR), and hydrogen chemisorptions/pulse reoxidation. Results indicated that both La2O3 and TiO2 doped supports facilitated the reduction of cobalt oxide species in reference to pure alumina supported cobalt catalysts, however further investigation is needed to determine the effect of ZrO2 on the reduction profile. Results showed an increased corrected cluster size for all three doped supported catalysts in comparison to their reference catalysts. The increase in reduction and an increase in the cluster size led to the conclusion that the support-metal interaction weakened by the addition of TiO2 and La2O3. It is also likely that the interaction decreased upon presence of ZrO2 on the alumina, but further research is necessary. Preliminary results have indicated that the alumina-supported catalysts with titanium oxide and lanthanum oxide present are of interest because of the weakened cobalt support interaction. These catalysts showed an increased extent of reduction, therefore more metallic cobalt is present on the support. However, whether or not there is more cobalt available to participate in the Fischer-Tropsch synthesis reaction (cobalt surface atoms) depends also on the cluster size. On one hand, increasing cluster size alone tends to decrease the active site density; on the other hand, by increasing the size of the cobalt clusters, there is less likelihood of forming oxidized cobalt complexes (cobalt aluminate) during Fischer-Tropsch synthesis. Thus, from the standpoint of stability, improving the extent of reduction while increasing the particle size slightly may be beneficial for maintaining the sites, even if there is a slight decrease in overall initial active site density.

Klettlinger, Jennifer Lindsey Suder↗
NASA NTRS2017

Refractory Organics in Comet 67P Churyumov-Gerasimenko: Additional Evidence for Large-scale Mixing in the Primitive Solar Nebula?

The COSIMA instrument onboard the Rosetta spacecraft collected and analyzed samples of individual particles from the coma of Comet67P/ Churyumov-Gerasimenko. Initial results of the analysis of several particles have been presented elsewhere while analyses of the organic component of the dust particles has been shown to compare favor ably to laboratory spectra of IOM extracted from the Orguil and Murchison meteorites. Here we will compare the spectra of the same two particles to laboratory spectra of organic grain coatings produced via Surface Mediated Reactions of CO, H2 and N2 on amorphous iron silicate grains.

Refractory Organics↗
NASA NTRS2007

Nanoparticles modified with multiple organic acids

Surface-modified nanoparticles of boehmite, and methods for preparing the same. Aluminum oxyhydroxide nanoparticles are surface modified by reaction with selected amounts of organic acids. In particular, the nanoparticle surface is modified by reactions with two or more different carboxylic acids, at least one of which is an organic carboxylic acid. The product is a surface modified boehmite nanoparticle that has an inorganic aluminum oxyhydroxide core, or part aluminum oxyhydroxide core and a surface-bonded organic shell. Organic carboxylic acids of this invention contain at least one carboxylic acid group and one carbon-hydrogen bond. One embodiment of this invention provides boehmite nanoparticles that have been surface modified with two or more acids one of which additional carries at least one reactive functional group. Another embodiment of this invention provides boehmite nanoparticles that have been surface modified with multiple acids one of which has molecular weight or average molecular weight greater than or equal to 500 Daltons. Yet, another embodiment of this invention provides boehmite nanoparticles that are surface modified with two or more acids one of which is hydrophobic in nature and has solubility in water of less than 15 by weight. The products of the methods of this invention have specific useful properties when used in mixture with liquids, as filler in solids, or as stand-alone entities.

Cook, Ronald Lee↗
NASA NTRS2018

Development of a Detailed Surface Chemistry Framework in DSMC

A generalized finite-rate surface chemistry framework incorporating a comprehensive list of reaction mechanisms is developed and implemented into the Direct Simulation Monte Carlo (DSMC) solver SPARTA (Stochastic PArallel Rarefied-gas Time-accurate Analyzer). The various mechanisms include adsorption, desorption, Eley-Rideal (ER), and several types of Langmuir-Hinshelwood (LH) mechanisms. The approach is to stochastically model the various competing reactions occurring on a set of active sites. Both gas-surface (e.g., adsorption, ER) and pure-surface (e.g., desorption) reaction mechanisms are incorporated, and the framework also includes catalytic or surface altering mechanisms involving the participation of the bulk-phase species (e.g., bulk carbon atoms). Marschall and MacLean developed a general formulation in which multiple phases and surface sites are used and a similar convention is adopted in the current work. Expressions for the microscopic parameters of reaction probabilities (for gas-surface reactions) and frequencies (for pure-surface reactions) that are required for DSMC are derived from the surface properties and macroscopic parameters such as rate constants, sticking coefficients, etc. The energy and angular distributions of the products are specified according to the reaction type and input parameters. This framework also presents physically consistent procedures to accurately compute the reaction probabilities and frequencies in the case of multiple reactions. The result is a modeling tool with a wide variety of surface reactions characterized via user-specified reaction rate constants, surface properties and parameters.

Surface Chemistry↗
NASA NTRS1990

In situ analysis of CO during chemisorption and oxidation on graphite: Supported Pt by FTIR-microspectrometry

For chemisorption and oxidation on Pt/HOPG (highly-orientated pyrolytic) graphite, reflectance Fourier Transform Infrared (FTIR)-microspectrometry reveals a variable state and reactivity for CO. Even for model surface science systems, where surface heterogeneity is minimal, surface diffusion may be too slow relative to the reaction rate to avoid segregation of reactants into surface islands under steady-state conditions. Thus in CO oxidation on Pt (where the relevant surface diffusion coefficients are such that D sub O less than D sub CO) then reactant CO islands exists at the perimeters of which the surface reaction is thought to occur. Furthermore CO can chemisorb on metals in linear and bridge forms to extents which vary with precise faces predominantly exposed coverage, etc. Infrared has long been used to probe the nature of adsorbed CO on model film and heterogeneous surfaces, but it may now be that FTIR-microspectrometry will allow the state of this adsorbate and reactant to be investigated with a spatial resolution of 4.4 microns on model (and real) catalytic surfaces.

Self, Valerie A.↗
NASA NTRS1988

Heterogeneous reactions of N2O5 with H2O and HCl on ice surfaces - Implications for Antarctic ozone depletion

This paper reports on the measurements of reaction probabilities for heterogeneous reaction of N2O5 with H2O and HCl on ice surfaces at 195 K, using a fast-flow reactor coupled with a quadrupole mass spectrometer. The reaction probability for N2O5 on pure-water ice was found to be 0.028 + or - 0.011, with nitric acid in the solid phase as the sole product. In the presence of HCl in ice, the probability of N2O5 reaction was enhanced (to 0.037); the reaction produced, besides solid-phase nitric acid, ClNO2 and ClONO which were released into the gas phase within a few milliseconds. The latter two compounds can be readily photolyzed in the austral spring to form active chlorine which would remove stratospheric ozone. It is suggested that, since the polar stratospheric clouds are believed to contain HCl-ice mixture on the surface, the reactions of N2O5 on H2O/HCl particles is a major factor in the Antarctic springtime ozone depletion.

Leu, Ming-Taun↗
NASA NTRS2000

Large-Area Atomic Oxygen Facility Used to Clean Fire-Damaged Artwork

In addition to completely destroying artwork, fires in museums and public buildings can soil a displayed artwork with so much accumulated soot that it can no longer be used for study or be enjoyed by the public. In situations where the surface has not undergone extensive charring or melting, restoration can be attempted. However, soot deposits can be very difficult to remove from some types of painted surfaces, particularly when the paint is fragile or flaking or when the top surface of the paint binder has been damaged. Restoration typically involves the use of organic solvents to clean the surface, but these solvents may cause the paint layers to swell or leach out. Also, immersion of the surface or swabbing during solvent cleaning may move or remove pigment through mechanical contact, especially if the fire damage extends into the paint binder. A noncontact technique of removing organic deposits from surfaces was developed out of NASA research on the effects of oxygen atoms on various materials. Atomic oxygen is present in the atmosphere surrounding the Earth at the altitudes where satellites typically orbit. It can react chemically with surface coatings or deposits that contain carbon. In the reaction, the carbon is converted to carbon monoxide and some carbon dioxide. Water vapor is also a byproduct of the reaction if the surface contains carbon-hydrogen bonds. To study this reaction, NASA developed Earth-based facilities to produce atomic oxygen for material exposure and testing. A vacuum facility designed and built by the Electro-Physics Branch of the NASA Glenn Research Center at Lewis Field to provide atomic oxygen over a large area for studying reactions in low Earth orbit has been used to successfully clean several full-size paintings. (This facility can accommodate paintings up to 1.5 by 2.1 m. The atomic oxygen plasma is produced between two large parallel aluminum plates using a radiofrequency power source operating at roughly 400 W. Atomic oxygen is generated uniformly over this area at an operating pressure of 1 to 5 mtorr.

Rutledge, Sharon K.↗
NASA NTRS2000

Rhenium/Oxygen Interactions at Elevated Temperatures

The oxidation of pure rhenium is examined from 600-1400 C in oxygen/argon mixtures. Linear weight loss kinetics are observed. Gas pressures, flow rates, and temperatures are methodically varied to determine the rate controlling steps. The reaction at 600 and 800 C appears to be controlled by a chemical reaction step at the surface; whereas the higher temperature reactions appear to be controlled by gas phase diffusion of oxygen to the rhenium surface. Attack of the rhenium appears to be along grain boundaries and crystallographic planes.

Jacobson, Nathan↗
NASA NTRS2012

Transformation of Graphitic and Amorphous Carbon Dust to Complex Organic Molecules in a Massive Carbon Cycle in Protostellar Nebulae

More than 95% of silicate minerals and other oxides found in meteorites were melted, or vaporized and recondensed in the Solar Nebula prior to their incorporation into meteorite parent bodies. Gravitational accretion energy and heating via radioactive decay further transformed oxide minerals accreted into planetesimals. In such an oxygen-rich environment the carbonaceous dust that fell into the nebula as an intimate mixture with oxide grains should have been almost completely converted to CO. While some pre-collapse, molecular-cloud carbonaceous dust does survive, much in the same manner as do pre-solar oxide grains, such materials constitute only a few percent of meteoritic carbon and are clearly distinguished by elevated D/H, N-15/N-16, C-13/C-12 ratios or noble gas patterns. Carbonaceous Dust in Meteorites: We argue that nearly all of the carbon in meteorites was synthesized in the Solar Nebula from CO and that this CO was generated by the reaction of carbonaceous dust with solid oxides, water or OH. It is probable that some fraction of carbonaceous dust that is newly synthesized in the Solar Nebula is also converted back into CO by additional thermal processing. CO processing might occur on grains in the outer nebula through irradiation of CO-containing ice coatings or in the inner nebula via Fischer-Tropsch type (FTT) reactions on grain surfaces. Large-scale transport of both gaseous reaction products and dust from the inner nebula out to regions where comets formed would spread newly formed carbonaceous materials throughout the solar nebula. Formation of Organic Carbon: Carbon dust in the ISM might easily be described as inorganic graphite or amorphous carbon, with relatively low structural abundances of H, N, O and S . Products of FTT reactions or organics produced via irradiation of icy grains contain abundant aromatic and aliphatic hydrocarbons. aldehydes, keytones, acids, amines and amides.. The net result of the massive nebular carbon cycle is to convert relatively inert carbonaceous dust from the ISM into the vital organic precursors to life such as amino acids and sugars intimately mixed with dust and ice in primitive planetesimals. Since the number of carbon atoms entering the Solar Nebula as dust exceeds the number of atoms entering the nebula as oxide grains. the formation of large quantities of complex organic molecules may represent the largest single chemical cycle in the nebula.

Nuth, Joseph A., III↗
NASA NTRS1975

A generalized expression for lag-time in the gas-phase permeation of hollow tubes

A generalized expression for the nonsteady-state parameter, lag-time, has been obtained from Fick's second law for gas-phase transport through hollow, cylindrical membranes. This generalized expression is simplified for three limiting cases of practical interest: (1) diffusion controlled transport, (2) phase boundary reaction control at the inlet surface, and (3) phase boundary reaction control at the outlet surface. In all three cases the lag-time expressions were found to be inversely proportional only to the diffusion coefficient and functionally dependent on the membrane radii. Finally, the lag-time expressions were applied to experimentally obtained lag-time data for alpha-phase titanium and alpha-phase iron.

Shah, K. K.↗
NASA NTRS2001

Physical State of Ices in the Outer Solar System

Comparison of the identity and abundances of ices observed around protostars and those associated with comets clearly suggests that comets preserve the heritage of the interstellar materials that aggregated to form them. However, the ability to identify these same species on icy satellites in the outer solar system is a complex function of the composition of the original ices, their subsequent thermal histories, and their exposure to various radiation environments. Our ability to identify the ices currently present on objects in the outer solar system relies upon observational and laboratory, and theoretical efforts. To date there is ample observational evidence for crystalline water ice throughout the outer solar system. In addition, there is growing evidence that amorphous ice may be present on some bodies. More volatile ices, e.g. N2, CH4. CO, and other species, e.g. ammonia hydrate, are identified on objects lying at and beyond Uranus. Both photolysis and radiolysis play important roles in altering the original surfaces due to chemical reactions and erosion of the surface. Ultraviolet photolysis appears to dominate alteration of the upper few hundred Angstroms, although sputtering the surface can sometimes be a significantly competitative process; dominating on icy surfaces embedded in a strong planetary magnetospheric field. There is growing observational evidence that the by-products of photolysis and radiolysis, suggested on a theoretical basis, are present on icy surfaces.

Roush, Ted L.↗
NASA NTRS2000

Deep Etching Process Developed for the Fabrication of Silicon Carbide Microsystems

Silicon carbide (SiC), because of its superior electrical and mechanical properties at elevated temperatures, is a nearly ideal material for the microminiature sensors and actuators that are used in harsh environments where temperatures may reach 600 C or greater. Deep etching using plasma methods is one of the key processes used to fabricate silicon microsystems for more benign environments, but SiC has proven to be a more difficult material to etch, and etch depths in SiC have been limited to several micrometers. Recently, the Sensors and Electronics Technology Branch at the NASA Glenn Research Center at Lewis Field developed a plasma etching process that was shown to be capable of etching SiC to a depth of 60 mm. Deep etching of SiC is achieved by inductive coupling of radiofrequency electrical energy to a sulfur hexafluoride (SF6) plasma to direct a high flux of energetic ions and reactive fluorine atoms to the SiC surface. The plasma etch is performed at a low pressure, 5 mtorr, which together with a high gas throughput, provides for rapid removal of the gaseous etch products. The lateral topology of the SiC microstructure is defined by a thin film of etch-resistant material, such as indium-tin-oxide, which is patterned using conventional photolithographic processes. Ions from the plasma bombard the exposed SiC surfaces and supply the energy needed to initiate a reaction between SiC and atomic fluorine. In the absence of ion bombardment, no reaction occurs, so surfaces perpendicular to the wafer surface (the etch sidewalls) are etched slowly, yielding the desired vertical sidewalls.

Beheim, Glenn M.↗
NASA NTRS2019

Effect of Mass Transfer on Aeroheating in Hypersonic Chemically Reacting Boundary Layers

Heat flux characterization of high-enthalpy boundary layer flows is key to optimize the performance and design of Thermal Protection System of next generation aerospace vehicles [1]. At atmospheric entry hypersonic speeds, ablation as well as surface catalycity impact boundary layer aeroheating. Out-gassing occurring from an ablative surface in planetary entry environment introduces a rich set of problems in thermodynamic, fluid dynamic, and material pyrolysis. Ablation leads to out-gassing and surface roughness, both of which are known to affect surface heating in hypersonic chemically reacting boundary layers via three main routes: gas blowing into the boundary layer from the wall, changing the surface heat transfer due to wall-flow chemical reactions, and modifying surface roughness via ablative processes.

Karimi, Mona↗
NASA NTRS2019

Effect of Out-Gassing on the Onset of Hypersonic Boundary Layer Transition

Prediction and control of the onset of transition and the associated variation in aerothermodynamic parameters in high-speed flows is key to optimize the performance and design of Thermal Protection Systems (TPS) of next-generation aerospace vehicles [1]. Boundary Layer Transition (BLT) characteristics can influence the surface heating budget determining the TPS thickness and consequently its weight penalty. Ablative heatshields are designed to alleviate the high heat flux at the surface through pyrolysis of their polymeric matrix and subsequent fiber ablation [2]. Pyrolysis leads to out-gassing and non-uniform ablation lead to surface roughness, both of which are known to influence the transition process. An ablator impacts BLT through three main routes: gas injecting into the boundary layer from the wall, changing the surface heat transfer due to wall-flow chemical reactions, and modifying surface roughness [3]. In preparation to Mars 2020 mission post-flight analysis, the predictive transition capability has been initiated toward hard-coupling porous material response analysis and aerothermal environment calculation.

Karimi, Mona↗
NASA NTRS2016

Evaluating Secondary Inorganic Aerosols in Three Dimensions

The spatial distribution of aerosols and their chemical composition dictates whether aerosols have a cooling or a warming effect on the climate system. Hence, properly modeling the three-dimensional distribution of aerosols is a crucial step for coherent climate simulations. Since surface measurement networks only give 2-D data, and most satellites supply integrated column information, it is thus important to integrate aircraft measurements in climate model evaluations. In this study, the vertical distribution of secondary inorganic aerosol (i.e., sulfate, ammonium, and nitrate) is evaluated against a collection of 14 AMS flight campaigns and surface measurements from 2000 to 2010 in the USA and Europe. GISS ModelE2 is used with multiple aerosol microphysics (MATRIX, OMA) and thermodynamic (ISORROPIA II, EQSAM) configurations. Our results show that the MATRIX microphysical scheme improves the model performance for sulfate, but that there is a systematic underestimation of ammonium and nitrate over the USA and Europe in all model configurations. In terms of gaseous precursors, nitric acid concentrations are largely underestimated at the surface while overestimated in the higher levels of the model. Heterogeneous reactions on dust surfaces are an important sink for nitric acid, even high in the troposphere. At high altitudes, nitrate formation is calculated to be ammonia limited. The underestimation of ammonium and nitrate in polluted regions is most likely caused by a too simplified treatment of the NH3/NH4(+) partitioning which affects the HNO3/NO3(-) partitioning.

aerosols↗