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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 109 records · Page 6

Oxidation of chemically-vapor-deposited silicon nitride and single-crystal silicon

The present 1000 C and 1300 C oxidation tests on 111-oriented single-crystal Si and dense CVD Si3N4 notes the oxidation rates of the latter in wet O2, dry O2, wet inert gas, and steam atmosphere conditions to be several orders of magnitude lower than the rates for the former in identical atmospheric conditions. Although the parabolic rate constant for Si increased linearly as the water vapor pressure increased, the parabolic rate constant for Si3N4 exhibited a nonlinear dependency on water vapor pressure in the presence of O2. NO and NH3 formation at the reaction interface of Si3N4, and the counterpermeation of these reaction products, are noted to dominate reaction kinetics.

Choi, Doo J.↗

The ultraviolet photochemistry of diacetylene - Direct detection of primary products of the metastable C4H2* + C4H2 reaction

The products of diacetylene's ultraviolet photochemistry over the 245-220 nm region were directly determined in experiments where C4H2 was excited within a small reaction tube attached to a pulsed nozzle. The products formed in the collisions of C4H2* with C4H2 were subsequently ionized by vacuum UV radiation (at 118 nm) in the ion source of a time-of-flight mass spectrometer. It was found that the reaction of C4H2* with C4H2 produces C6H2 (+C2H2), C8H2 (+2H,H2), and C8H3 (+H), confirming the results of Glicker and Okabe (1987). Under certain conditions, secondary products were observed. Mechanisms for the observed reactions are proposed.

Bandy, Ralph E.↗

Manufacturing Ethyl Acetate From Fermentation Ethanol

Conceptual process uses dilute product of fermentation instead of concentrated ethanol. Low-concentration ethanol, extracted by vacuum from fermentation tank, and acetic acid constitutes feedstock for catalytic reaction. Product of reaction goes through steps that increases ethyl acetate content to 93 percent by weight. To conserve energy, heat exchangers recycle waste heat to preheat process streams at various points.

Rohatgi, Naresh K.↗

Reactions of O/1D/ with methane and ethane.

Mixtures of nitrous oxide and methane and mixtures of nitrous oxide and ethane were photolyzed with 1849-A light. The reaction products were analyzed chromatographically. It was found that the reaction of the excited atomic oxygen with methane gives mainly CH3 and OH radicals as initial products, along with about 9% of formaldehyde and molecular hydrogen. The reaction of the excited atomic oxygen with ethane gives C2H5, OH, CH3 and CH2OH as major initial products, with only a few per cent of molecular hydrogen.

Lin, C.-L.↗

Contamination Detection and Mitigation Strategies for Unsymmetric Dimethylhydrazine/Nitrogen Tetroxide Non-Combustion Product Residues

Dimethylamine and nitrite, which are non-combustion reaction products of unsymmetrical dimethylhydrazine (UDMH) and nitrogen tetroxide (NTO) propellants, can contaminate spacesuits during extra-vehicular activity (EVA) operations. They can react with water in the International Space Station (ISS) airlock to form N-nitrosodimethylamine (NDMA), a carcinogen. Detection methods for assessing nitrite and dimethylamine contamination were investigated. The methods are based on color-forming reactions in which intensity of color is proportional to concentration. A concept color detection kit using a commercially available presumptive field test for methamphetamine coupled with nitrite test strips was developed and used to detect dimethylamine and nitrite. Contamination mitigation strategies were also developed.

Greene, Benjamin↗

Silicon oxidation in fluoride solutions

Silicon is produced in a NaF, Na2SiF6, and Na matrix when SiF4 is reduced by metallic sodium. Hydrogen is evolved during acid leaching to separate the silicon from the accompanying reaction products, NaF and Na2SiF6. The hydrogen evolution reaction was studied under conditions simulating leaching conditions by making suspensions of the dry silicon powder in aqueous fluoride solutions. The mechanism for the hydrogen evolution is discussed in terms of spontaneous oxidation of silicon resulting from the cooperative effects of (1) elemental sodium in the silicon that reacts with water to remove a protective silica layer, leaving clean reactive silicon, and (2) fluoride in solution that complexes with the oxidized silicon in solution and retards formation of a protective hydrous oxide gel.

Sancier, K. M.↗

A signature of auroral precipitation in the nightside ionosphere of Venus

It is shown that the densities of mass-28 ions measured by the Pioneer Venus Orbiter ion mass spectrometer (OIMS) on the nightside of Venus are highly variable and show little correlation with the values of the O(+) densities. The total production rates of mass-28 ions in the chemical equilibrium region are determined and it is found that this production rate cannot be explained by known chemical production reactions. It is proposed that the 'excess' production is due to precipitation of electrons into the nightside thermosphere.

Fox, J. L.↗

Atomic Oxygen Environment and Effects Overview

Atomic oxygen is the most predominant constituent in the low Earth orbital environment between the altitudes of 180 and 650 km. It is also a major constituent of the Mars orbital environment. It is very chemically reactive and can oxidize many spacecraft surfaces to form volatile reaction products. The importance of understanding atomic oxygen reactions with materials has led to both flight experiments in low Earth orbit and ground-based testing in vacuum chambers containing atomic oxygen to study its’ effect on materials. Testing has been performed in order to determine the extent of the atomic oxygen reaction and assess material and component durability. In addition, the effectiveness of mitigation techniques such as application of a protective coating, adding fillers, or using shielding and getter materials has also been studied both in flight and ground-based experiments. This presentation will focus on defining atomic oxygen environments, discussing its effect on spacecraft materials, and describing some of the testing and mitigation techniques that have been investigated.

Atomic Oxygen, Low Earth Orbit, Low Mars Orbit, ox↗

Prebiotic synthesis of histidine

The prebiotic formation of histidine (His) has been accomplished experimentally by the reaction of erythrose with formamidine followed by a Strecker synthesis. In the first step of this reaction sequence, the formation of imidazole-4-acetaldehyde took place by the condensation of erythrose and formamidine, two compounds that are known to be formed under prebiotic conditions. In a second step, the imidazole-4-acetaldehyde was converted to His, without isolation of the reaction products by adding HCN and ammonia to the reaction mixture. LC, HPLC, thermospray liquid chromatography-mass spectrometry, and tandem mass spectrometry were used to identify the product, which was obtained in a yield of 3.5% based on the ratio of His/erythrose. This is a new chemical synthesis of one of the basic amino acids which had not been synthesized prebiotically until now.

Non-NASA Center↗

Abrasion-ablation model for neutron production in heavy ion reactions

In heavy ion reactions, neutron production at forward angles is observed to occur with a Gaussian shape that is centered near the beam energy and extends to energies well above that of the beam. This paper presents an abrasion-ablation model for making quantitative predictions of the neutron spectrum. To describe neutrons produced from the abrasion step of the reaction where the projectile and target overlap, the authors use the Glauber model and include effects of final-state interactions. They then use the prefragment mass distribution from abrasion with a statistical evaporation model to estimate the neutron spectrum resulting from ablation. Measurements of neutron production from Ne and Nb beams are compared with calculations, and good agreement is found.

Cucinotta, Francis A.↗

Abiotic formation of hydrocarbons and oxygenated compounds during thermal decomposition of iron oxalate

The formation of organic compounds during the decomposition of iron oxalate dihydrate (IOD) was investigated as a possible analog for abiotic organic synthesis in geological systems. After heating at 330 degrees C for 2-4 days, IOD decomposed to a mixture of the minerals siderite and magnetite plus gas and non-volatile organic compounds. The organic products included an extremely large variety of compounds, making identification of individual reaction products difficult. However, the non-volatile products were dominated by several homologous series of alkylated cyclic compounds mostly containing a single aromatic ring, including alkylphenols, alkylbenzenes, alkyltetrahydronaphthols, and alkyltetrahydronaphthalenes. Traces of n-alkanols, n-alkanoic acids, n-alkanones, and n-alkanes were also identified. Carbon in the gas phase was predominantly CO2 (+CO?), with lesser amounts of light hydrocarbons to > C6 including all possible branched and normal isomers of the alkanes and alkenes. The organic products were apparently the result of two concurrent reaction processes: (1) condensation of the two-carbon units present in the initial oxalate moiety, and (2) Fischer-Tropsch-type synthesis from CO2 or CO generated during the experiment. Compounds produced by the former process may not be characteristic of synthesis from the single-carbon precursors which predominate in geologic systems, suggesting iron oxalate decomposition may not provide a particularly suitable analog for investigation of abiotic organic synthesis. When water was included in the reaction vessels, CO2 and traces of methane and light hydrocarbon gases were the only carbon products observed (other than siderite), suggesting that the presence of water allowed the system to proceed rapidly towards equilibrium and precluded the formation of metastable organic intermediates.

Non-NASA Center↗

Quantifying VOC-Reaction Tracers, Ozone Production, and Continuing Aerosol Production Rates in Urban and Far-Downwind Atmospheres

We have found a surprisingly informative decomposition of the complex question of smoggy ozone production (basically, [HO2] in a more locally determined field of [NO]) in the process of linked investigations of modestly smoggy Eastern North America (by NASA aircraft, July 2004) and rather polluted Flushing, NYC (Queens College, July, 2001). In both rural and very polluted situations, we find that a simple contour graph parameterization of the local principal ozone production rate can be estimated using only the variables [NO] and j(sub rads) [HCHO]: Po(O3) = c (j(sub rads) [HCHO])(sup a) [HCHO](sup b). Here j(sub rads) is the photolysis of HCHO to radicals, presumably capturing many harder-UV photolytic processes and the principle ozone production is that due to HO2; mechanisms suggest that ozone production due to RO2 is closely correlated, often suggesting a limited range of different proportionality factors. The method immediately suggests a local interpretation for concepts of VOC limitation and NOx limitation. We believe that the product j(sub rads) [HCHO] guages the oxidation rate of observed VOC mixtures in a way that also provides [HO2] useful for the principle ozone production rate k [HO2] [NO], and indeed, all ozone chemical production. The success of the method suggests that dominant urban primary-HCHO sources may transition to secondary plume-HCHO sources in a convenient way. Are there other, simple, near-terminal oxidized VOC's which help guage ozone production and aerosol particle formation? Regarding particles, we report on, to the extent NASA Research resources allow, on appealing relationships between far-downwind (Atlantic PBL) HCHO and very fine aerosol (including sulfate. Since j(sub rads) [HCHO] provides a time-scale, we may understand distant-plume particle production in a more quantitative manner. Additionally we report on a statistical search in the nearer field for relationships between glyoxals (important near-terminal aromatic and isoprene reaction products) and aerosol production, looking for VOC's that might be most implicated. All three variables j(sub rads), [HCHO], and [NO] are relatively easily measured in widespread air pollution monitoring networks, and all are deducible form space-borne observations, though estimation of [NO] from [NO2] (the species observable from space) may require care. We report also on airborne and surface observations of HCHO, suggesting that concentrated (urban) and more diffuse (forest) sources may be distinguishable from space. The use of the 3.58 micron microwindow for HCHO remote sensing should allow much sharper resolution of HCHO than the UV. UV sensing requires large and expensive instruments, but even these seem justified since formaldehyde is so informative.

Chatfield, Robert↗

Photocatalytic generation of hydrogen from water

A concept designed to overcome the problems encountered when using photodissociation for the generation of hydrogen is discussed. The problems limiting the efficiency of photodissociation of water are the separation of the photolysis products and the high energy photons necessary for the reaction. It is shown that the dissociation energy of a large number of molecules is catalytically reduced when these molecules are in intimate contact with the surface of certain metals. It is proposed to develop a surface which will take advantage of this catalytic shift in dissociation energies to reduce the photon energy required to produce hydrogen. This same catalytic surface can be used to separate the reaction products if it is made so that one of the dissociations products is soluble in the metal and others are not. This condition is met by many metal systems such as platinum group metals which have been used commercially to separate hydrogen from other gases and liquids.

Bottoms, W. R.↗

Amino Acids from Icy Amines: A Radiation-Chemical Approach to Extraterrestrial Synthesis

Detections of amino acids in meteorites go back several decades, with at least 100 such compounds being reported for the Murchison meteorite alone. The presence of these extraterrestrial molecules raises questions as to their formation, abundance, thermal stability, racemization, and possible subsequent reactions. Although all of these topics have been studied in laboratories, such work often involves many variables and unknowns. This has led us to seek out model systems with which to uncover reaction products, test chemical predictions, and sited light on underlying reaction mechanisms. This presentation will describe one such study, focusing on amino-acid formation in ices.

Dworkin, J. P.↗

Experiments concerning the laser-enhanced reaction between vibrationally excited O3 and NO

The enhancement in reaction rate between O3 and NO is studied for the case of O3 vibrationally excited by a CO2 laser. Chemiluminescence observations of a vibrationally excited and an electronically excited nitrogen dioxide reaction product provide information on the separate contributions to the overall reaction rate of these two reactive channels. The contribution of the stretching and bending modes of O3 to the reaction rate enhancement is also discussed. In addition, consideration is given to the nonreactive vibrational deactivation of vibrationally excited O3.

Hui, K.-K.↗

The catalysis of nucleotide polymerization by compounds of divalent lead

The nonenzymatic, nontemplate catalysis of nucleotide polymerization by Pb(2+) ions, a possible prebiotic catalyst, is reported. Adenosine and uridine phosphoimidazoles were reacted in buffered solutions of lead salts and products were analyzed by means of paper chromatography and electrophoresis. In the presence of Pb(2+) ion at pH 8.0 and 7.0 the reaction is found to progress rapidly with excellent yields of oligomers, with optimal yields observed at pH 8.0. Little temperature dependence in the range 0 to 30 C is observed, however hydrolysis of the reaction products is minimal when the reaction is carried out at 0 C. Results show that the yield of oligomers is insensitive to mixing or the source of lead ions, indicating that naturally occurring minerals or precipitates could be a source of Pb(2+) ions under prebiotic conditions.

Sleeper, H. L.↗