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At least 73 records · Page 4

Corrosion-Prevention Capabilities of a Water-Borne, Silicone-Based, Primerless Coating

Comparative tests have been performed to evaluate the corrosion-prevention capabilities of an experimental paint of the type described in Water-Borne, Silicone-Based, Primerless Paints, NASA Tech Briefs, Vol. 26, No. 11 (November 2002), page 30. To recapitulate: these paints contain relatively small amounts of volatile organic solvents and were developed as substitutes for traditional anticorrosion paints that contain large amounts of such solvents. An additional desirable feature of these paints is that they can be applied without need for prior application of primers to ensure adhesion. The test specimens included panels of cold-rolled steel, stainless steel 316, and aluminum 2024-T3. Some panels of each of these alloys were left bare and some were coated with the experimental water-borne, silicone-based, primerless paint. In addition, some panels of aluminum 2024-T3 and some panels of a fourth alloy (stainless steel 304) were coated with a commercial solvent-borne paint containing aluminum and zinc flakes in a nitrile rubber matrix. In the tests, the specimens were immersed in an aerated 3.5-weight-percent aqueous solution of NaCl for 168 hours. At intervals of 24 hours, the specimens were characterized by electrochemical impedance spectroscopy (EIS) and measurements of corrosion potentials. The specimens were also observed visually. As indicated by photographs of specimens taken after the 168-hour immersion (see figure), the experimental primerless silicone paint was effective in preventing corrosion of stainless steel 316, but failed to protect aluminum 2024-T3 and cold-rolled steel. The degree of failure was greater in the case of the cold-rolled steel. On the basis of visual observations, EIS, and corrosion- potential measurements, it was concluded that the commercial aluminum and zinc-filled nitrile rubber coating affords superior corrosion protection to aluminum 2024-T3 and is somewhat less effective in protecting stainless steel 304.

Calle, Luz Marina↗

Isotopic Anomalies in Primitive Solar System Matter: Spin-State-Dependent Fractionation of Nitrogen and Deuterium in Interstellar Clouds

Organic material found in meteorites and interplanetary dust particles is enriched in D and N-15. This is consistent with the idea that the functional groups carrying these isotopic anomalies, nitriles and amines, were formed by ion-molecule chemistry in the protosolar nebula, Theoretical models of interstellar fractionation at low temperatures predict large enrichments in both D and N-15 and can account for the largest isotopic enrichments measured in carbonaceous meteorites. However, more recent measurements have shown that, in some primitive samples, a large N-15 enrichment does not correlate with one in D, and that some D-enriched primitive material displays little, if any, N-15 enrichment. By considering the spin-state dependence in ion-molecule reactions involving the ortho and para forms of H2, we show that ammonia and related molecules can exhibit such a wide range of fractionation for both N-15 and D in dense cloud cores. We also show that while the nitriles, HCN and HNC, contain the greatest N=15 enrichment, this is not expected to correlate with extreme D enrichment. These calculations therefore support the view that solar system N-15 and D isotopic anomalies have an interstellar heritage. We also compare our results to existing astronomical observations and briefly discuss future tests of this model.

Wirstrom, Eva S.↗

Isotopic Anomalies in Primitive Solar System Matter: Spin-State Dependent Fractionation of Nitrogen and Deuterium in Interstellar Clouds

Organic material found in meteorites and interplanetary dust particles is enriched in D and N-15, This is consistent with the idea that the functional groups carrying these isotopic anomalies, nitriles and amines, were formed by ion-molecule chemistry in the protosolar core. Theoretical models of interstellar fractionation at low temperatures predict large enrichments in both D and N-15 and can account for the largest isotop c enrichments measured in carbonaceous meteorites, However, more recent measurements have shown that, in some primitive samples, a large N-15 enrichment does not correlate with one in D, and that some D-enriched primitive material displays little, if any, N-15 enrichment. By considering the spin-state dependence in ion-molecule reactions involving the ortho and para forms of H2, we show that ammonia and related molecules can exhibit such a wide range of fractionation for both N-15 and D in dense cloud cores, We also show that while the nitriles, HCN and HNC, contain the greatest N-15 enrichment, this is not expected to correlate with extreme D emichment. These calculations therefore support the view that Solar System N-15 and D isotopic anomalies have an interstellar heritage, We also compare our results to existing astronomical observations and briefly discuss future tests of this model.

Wirstrom, Eva S.↗

Observations of Organic Chemistry on Titan

Titan is the largest moon of Saturn, with a thick (1.45 bar) atmosphere composed primarily of molecular nitrogen and methane. Atmospheric photochemistry results in the production of a wide range of complex organic molecules, including hydrocarbons, nitriles, aromatics and species of possible pre-biotic relevance. Studies of Titan's atmospheric chemistry thus provide a unique opportunity to explore the origin and evolution of complex organic matter in a primitive (terrestrial) planetary atmosphere. Underpinned by laboratory measurements, remote and in-situ observations of hydrocarbons, nitriles and oxygen-bearing species provide important new insights in this regard. The Atacama Large Millimeter/submillimeter Array (ALMA) is a powerful new facility, well suited to the study of molecular emission from Titan's upper and middle-atmosphere. This presentation will focus on detection and mapping of rotational emission lines from molecules including HNC, CO, HC3N, CH3CN, C2H3CN and C2H5CN, as well minor isotopologues. Possible chemical formation pathways for these species will be discussed, and the scope for improved understanding of non-aqueous organic chemistry through laboratory experiments and atmospheric/liquid-phase simulations under Titan-like conditions will be examined [5].

Charnley, Steven B.↗

X-Ray Absorption near Edge Structure Spectroscopic Study of Hayabusa Category 3 Carbonaceous Particles

Analyses with a scanning transmission x-ray microscope (STXM) using x-ray absorption near edge structure (XANES) spectroscopy were applied for the molecular characterization of two kinds of carbonaceous particles of unknown origin, termed category 3, which were collected from the Hayabusa spacecraft sample catcher. Carbon-XANES spectra of the category 3 particles displayed typical spectral patterns of heterogeneous organic macromolecules; peaks corresponding to aromatic/olefinic carbon, heterocyclic nitrogen and/or nitrile, and carboxyl carbon were all detected. Nitrogen-XANES spectra of the particles showed the presence of N-functional groups such as imine, nitrile, aromatic nitrogen, amide, pyrrole, and amine. An oxygen-XANES spectrum of one of the particles showed a ketone group. Differences in carbon- and nitrogen-XANES spectra of the category 3 particles before and after transmission electron microscopic (TEM) observations were observed, which demonstrates that the carbonaceous materials are electron beam sensitive. Calcium-XANES spectroscopy and elemental contrast mapping identified a calcium carbonate grain from one of the category 3 particles. No fluorine-containing molecular species were detected in fluorine-XANES spectra of the particles. The organic macromolecular features of the category 3 particles were distinct from commercial and/or biological ‘fresh (non-degraded)’ polymers, but the category 3 molecular features could possibly reflect degradation of contaminant polymer materials or polymer materials used on the Hayabusa spacecraft. However, an extraterrestrial origin for these materials cannot currently be ruled out.

Asteroides↗

Detection Opportunity for Aromatic Signature in Titan's Aerosols in the 4.1-5.3 μm Range

The Cassini/Huygens mission provided new insights on the chemistry of the upper atmosphere of Titan. The presence of large molecules and ions (>100's of amu) detected by Cassini at high altitude was not expected, and questions the original assumptions regarding the aerosol formation pathways. From recent laboratory studies, it has been shown that the inclusion of trace amounts of aromatic species drastically impacts the chemistry of aerosol formation and induces observable changes in the properties of the aerosols. In this Letter we focus on the effect of one of the simplest nitrogenous aromatics, pyridine (C5H5N), on the infrared signature of Titan's aerosol analogs. We introduce initial gas mixtures of (i) N2–C5H5N (100%/250 ppm), (ii) N2–CH4–C5H5N (99%/1%/250 ppm), and (iii) N2–CH4 (99%/1%) in a cold plasma discharge. The material produced, herein called tholins, is then analyzed by mid-infrared spectroscopy. When adding pyridine in the discharge, the tholins produced present an aromatic signature in the 4.1–5.3 μm (1850–2450 cm−1) spectral region, attributed to overtones of aromatic C–H out-of-plane bending vibrations. We also observe a spectral shift of the nitrile and iso-nitrile absorption band with the inclusion of pyridine in the gas mixture. These results could help to investigate the data obtained at Titan by the Cassini/Visual and Infrared Mapping Spectrometer (VIMS) instrument in the 1–5 μm infrared window.

Mathé, Christophe↗

The Titan Haze Simulation (THS) Experiment on COSmIC. Part III. XANES Study of Laboratory Analogs of Titan Tholins

We have used the Titan Haze Simulation (THS) experimental set-up at NASA Ames’ COSmIC 19 facility to produce four laboratory analogs of Titan’s aerosols, or tholins. These tholin samples 20 were produced from four gas mixtures, representative of Titan’s atmosphere, of initial 21 compositions N2:CH4 (90:10 and 95:5) and N2:CH4:C2H2 (89.5:10:0.5 and 94.5:5:0.5) at 150 K, 22 using a plasma discharge in the stream of a jet-cooled gas expansion. Here we present an ex-situ 23 X-ray absorption near-edge structure (XANES) spectroscopy analysis of these four tholin 24 samples. The C- and N-XANES spectra show the presence of various functional groups 25 (aromatic carbon, imines, nitriles, etc.) whose abundances are correlated with (i) the relative 26 proportions between N2 and CH4, and (ii) the presence or absence of C2H2 in the initial mixtures. 27 In particular, mixtures containing C2H2 result in the formation of tholins consisting of more 28 aromatic structures and displaying larger relative amounts of imines and nitriles, but lower 29 overall nitrogen content. XANES spectroscopy also allowed for the determination of the 30 elemental C/N ratios for the four tholins, which were all found to be low (< 2.5) and consistent 31 with those measured for tholins produced in other, independent experimental set-ups. The C/N 32 ratios of tholins produced from gas mixtures that contained C2H2 (2.2–2.4) were found to be 33 about twice as large as those of tholins produced from gas mixtures that did not contain C2H234 (0.9–1.3). These new experimental results from the COSmIC/THS experiment demonstrate the 35 impact initial precursors have on the nitrogen chemistry during the formation of tholins, which 36 may help in the interpretation of observations and the development of models of Titan’s 37 atmosphere.

Titan↗

Intensive Titan exploration begins

The Cassini Orbiter spacecraft first skimmed through the tenuous upper atmosphere of Titan on 26 October 2004. This moon of Saturn is unique in our solar system, with a dense nitrogen atmosphere that is cold enough in places to rain methane, the feedstock for the atmospheric chemistry that produces hydrocarbons, nitrile compounds, and Titan's orange haze. The data returned from this flyby supply new information on the magnetic field and plasma environment around Titan, expose new facets of the dynamics and chemistry of Titan's atmosphere, and provide the first glimpses of what appears to be a complex, fluid-processed, geologically young Titan surface.

Spacecraft↗

Fire retardant polyisocyanurate foam

Fire retardant properties of low density polymer foam are increased. Foam has pendant nitrile groups which form thermally-stable heterocyclic structures at temperature below degradation temperature of urethane linkages.

Riccitiello, S. R.↗

Experimental interstellar organic chemistry: Preliminary findings

In a simulation of interstellar organic chemistry in dense interstellar clouds or on grain surfaces, formaldehyde, water vapor, ammonia and ethane are deposited on a quartz cold finger and ultraviolet-irradiated in high vacuum at 77K. The HCHO photolytic pathway which produces an aldehyde radical and a superthermal hydrogen atom initiates solid phase chain reactions leading to a range of new compounds, including methanol, ethanol, acetaldehyde, acetonitrile, acetone, methyl formate, and possibly formic acid. Higher nitriles are anticipated. Genetic relations among these interstellar organic molecules (e.g., the Cannizzaro and Tischenko reactions) must exist. Some of them, rather than being synthesized from smaller molecules, may be degradation products of larger organic molecules, such as hexamethylene tetramine, which are candidate consitituents of the interstellar grains. The experiments reported here may also be relevant to cometary chemistry.

Khare, B. N.↗

Experiments in Jovian atmosphere.

A 1000 ml reaction vessel, fitted with a stopcock, two joints for the electrodes, and a connecting joint, was used in the investigation. The flask, which has a cold finger at the bottom, was filled with an equimolar mixture of anhydrous methane and ammonia. The electrodes were adjusted to provide a gap of about 0.8 cm between them so that the current flowing through the electrodes was about 0.5 mA and a continuous spark could be observed. The operation was continued for 20 hr. The analysis of the reaction products showed the formation of amino nitriles under the conditions of the investigation.

Chadha, M. S.↗

Red clouds in reducing atmospheres

A dark reddish-brown high-molecular weight polymer is produced by long wavelength ultraviolet irradiation of abundant gases in reducing planetary atmospheres. The polymer is examined by paper chromatography, mass spectrometry, and infrared, visible, and ultraviolet spectroscopy. High carbon-number straight-chain alkanes with NH2 and, probably, OH and C = O groups are identified, along with amino acids. There are chemical similarities between this polymer and organic compounds recovered from carbonaceous chondrites and precambrian sediments. The visible and near-ultraviolet transmission spectrum of the polymer shows its absorption optical depth to be redder than lambda(-2) and perhaps similar in coloration to the clouds of Jupiter, Saturn, and Titan. The nitrile content is small, and the polymer should be semitransparent in the 5 micrometer atmospheric window. Such polymers may be a common constituent of clouds in the outer solar system and on the early earth.

Khare, B. N.↗

Interstellar molecules - Origin by catalytic reactions on grain surfaces

To determine the compound distribution formed by surface catalysis, mixtures of CO, D2, and ND2 were heated with nickel-iron or montmorillonite clay catalysts for 49-214 hours at 250 to 300 C. Compounds identified include most of the known polyatomic interstellar molecules, as well as homologous series of acetylenes, dienes, alcohols, aldehydes, ketones, ethers, esters, nitriles, amines, etc., and cyclic compounds such as furans and pyrroles. These homologous series are uniquely characteristic of surface catalysis. A search for the heavier members of these series, predicted to occur at 1/10th to 1/1,000th the abundance of the lightest members, thus comprises a crucial test of this mechanism.

Anders, E.↗

Aminonitriles - Possible role in chemical evolution

The formation of HCN, ammonium cyanide, alkylnitriles, aminoacetonitrile and its C- and N-methyl homologs was demonstrated earlier in a simulated Jovian atmosphere. The polymeric material resulting in these experiments was shown to give glycine, alanine, sarcosine, aspartic acid and some imino dibasic acids on acid hydrolysis, suggesting thereby the participation of the monomeric nitriles in the formation of the polymeric product(s). Further examination of products resulting from semicorona and arc discharge through a mixture of methane and ammonia has provided evidence for the formation of alkylaminopropionitriles as a complex mixture and also some pyridyl and pyrimidyl type heterocyclic compounds. A gas chromatograph/mass spectrometer examination of the heterocyclics showed resemblance with those found in some carbonaceous chondrites. The significance of these findings in relation to chemical evolution is discussed.

Chadha, M. S.↗

Photosynthesis of organic compounds in the atmosphere of Jupiter

An efficient conversion of CH4 to hydrocarbons and HCN takes place when NH3 is photolysed in the presence of CH4, H2, and He using a 184.9 nm light source. The extent of NH3 decomposition after a 1 hr exposure was determined spectrophotometrically; CH4, N2, and C2 and C3 hydrocarbons were detected and analyzed by mass spectrometry. Photolysis of one molar equivalent of NH3 results in the loss of 0.84 molar equivalent of CH4, which apparently reacts with hot hydrogen atoms produced by photolysis. The 8% of the NH3 which is not converted to N2 probably is converted to organic amines and nitrile derivatives. The results indicate that NH3 photolysis is a highly probable mechanism for the conversion of methane to more complex hydrocarbons in the upper atmosphere of Jupiter, and predict the occurrence of HCN, NH2NH2, and higher hydrocarbons in the Jovian atmosphere above the NH3 clouds.

Ferris, J. P.↗

Abiotic origin of biopolymers

A variety of methods have been investigated in different laboratories for the polymerization of amino acids and nucleotides under abiotic conditions. They include (1) thermal polymerization; (2) direct polymerization of certain amino acid nitriles, amides, or esters; (3) polymerization using polyphosphate esters; (4) polymerization under aqueous or drying conditions at moderate temperatures using a variety of simple catalysts or condensing agents like cyanamide, dicyandiamide, or imidazole; and (5) polymerization under similar mild conditions but employing activated monomers or abiotically synthesized high-energy compounds such as adenosine 5'-triphosphate (ATP). The role and significance of these methods for the synthesis of oligopeptides and oligonucleotides under possible primitive-earth conditions is evaluated. It is concluded that the more recent approach involving chemical processes similar to those used by contemporary living organisms appears to offer a reasonable solution to the prebiotic synthesis of these biopolymers.

Oro, J.↗