Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “model compounds”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
NASA NTRS1992

Studies of the kinetics and mechanisms of perfluoroether reactions on iron and oxidized iron surfaces

Polymeric perfluoroalkylethers are being considered for use as lubricants in high temperature applications, but have been observed to catalytically decompose in the presence of metals. X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD) were used to explore the decomposition of three model fluorinated ethers on clean polycrystalline iron surfaces and iron surfaces chemically modified with oxygen. Low temperature adsorption of the model fluorinated ethers on the clean, oxygen modified and oxidized iron surfaces was molecular. Thermally activated defluorination of the three model compounds was observed on the clean iron surface at remarkably low temperatures, 155 K and below, with formation of iron fluoride. Preferential C-F bond scission occurred at the terminal fluoromethoxy, CF3O, of perfluoro-1-methoxy-2-ethoxy ethane and perfluoro-1-methoxy-2-ethoxy propane and at CF3/CF2O of perfluoro-1,3-diethoxy propane. The reactivity of the clean iron toward perfluoroalkylether decomposition when compared to other metals is due to the strength of the iron fluoride bond and the strong electron donating ability of the metallic iron. Chemisorption of an oxygen overlayer lowered the reactivity of the iron surface to the adsorption and decomposition of the three model fluorinated ethers by blocking active sites on the metal surface. Incomplete coverage of the iron surface with chemisorbed oxygen results in a reaction which resembles the defluorination reaction observed on the clean iron surface. Perfluoro-1-methoxy-2-ethoxy ethane reacts on the oxidized iron surface at 138 K, through a Lewis acid assisted cleavage of the carbon oxygen bond, with preferential attack at the terminal fluoromethoxy, CF3O. The oxidized iron surface did not passivate, but became more reactive with time. Perfluoro-1-methoxy-2-ethoxy propane and perfluoro-1,3-diethoxy propane desorbed prior to the observation of decomposition on the oxidized iron surface.

Napier, Mary E.↗
NASA NTRS1993

Development of the Monolith Froth Reactor for Catalytic Wet Oxidation of CELSS Model Wastes

The aqueous phase oxidation of acetic acid, used as a model compound for the treatment of CELSS (Controlled Ecological Life Support System) waste, was carried out in the monolith froth reactor which utilizes two-phase flow in the monolith channels. The catalytic oxidation of acetic acid was carried out over a Pt/Al2O3 catalyst at temperatures and pressures below the critical point of water. The effect of externally controllable parameters (temperature, liquid flow rate, distributor plate orifice size, pitch, and catalyst distance from the distributor plate) on the rate of acetic acid oxidation was investigated. Results indicate reaction rate increased with increasing temperature and exhibited a maximum with respect to liquid flow rate. The apparent activation energy calculated from reaction rate data was 99.7 kJ/mol. This value is similar to values reported for the oxidation of acetic acid in other systems and is comparable to intrinsic values calculated for oxidation reactions. The kinetic data were modeled using simple power law kinetics. The effect of "froth" feed system characteristics was also investigated. Results indicate that the reaction rate exhibits a maximum with respect to distributor plate orifice size, pitch, and catalyst distance from the distributor plate. Fundamental results obtained were used to extrapolate where the complete removal of acetic acid would be obtained and for the design and operation of a full scale CELSS treatment system.

Fisher, John W.↗
NASA NTRS1995

Development of the Monolith Froth Reactor for Catalytic Wet Oxidation of CELSS Model Wastes

The aqueous phase oxidation of acetic acid, used as a model compound for the treatment of CELSS (Controlled Ecological Life Support System) waste, was carried out in the monolith froth reactor which utilizes two-phase flow in the monolith channels. The catalytic oxidation of acetic acid was carried out over a Pt/Al2O3 catalyst, prepared at The University of Tulsa, at temperatures and pressures below the critical point of water. The effect of externally controllable parameters (temperature, liquid flow rate, distributor plate orifice size, pitch, and catalyst distance from the distributor plate) on the rate of acetic acid oxidation was investigated. Results indicate reaction rate increased with increasing temperature and exhibited a maximum with respect to liquid flow rate. The apparent activation energy calculated from reaction rate data was 99.7 kJ/mol. This value is similar to values reported for the oxidation of acetic acid in other systems and is comparable to intrinsic values calculated for oxidation reactions. The kinetic data were modeled using simple power law kinetics. The effect of "froth" feed system characteristics was also investigated. Results indicate that the reaction rate exhibits a maximum with respect to distributor plate orifice size, pitch, and catalyst distance from the distributor plate. Fundamental results obtained were used to extrapolate where the complete removal of acetic acid would be obtained and for the design and operation of a full scale CELSS treatment system.

Abraham, Martin↗
NASA NTRS1993

Optical spectroscopy of a highly fluorescent aggregate of bacteriochlorophyll c

Bacteriochlorophyll (BChl) c and a similar model compound, Mg-methyl bacteriopheophorbide d, form several types of aggregates in nonpolar solvents. One of these aggregates is highly fluorescent, with a quantum yield higher than that of the monomer. This aggregate is also unusual in that it shows a rise time in its fluorescence emission decay at certain wavelengths, which is ascribed to a change in conformation of the aggregate. An analysis of fluorescence depolarization data is consistent with either a linear aggregate of four or five monomers or preferably a cyclic arrangement of three dimers.

NASA Discipline Exobiology↗
NASA NTRS1972

Quantitation of buried contamination by use of solvents. Part 1: Solvent degradation of amine cured epoxy resins

The solubility and/or swelling of cured epoxy resins was studied using the solubility parameter method. Determination of solubility parameters were found in order to select solvents for solvent-assisted degradation of cured epoxy polymers used in spacecraft. A method for improving recovery of seeded spores is suggested for assay of buried contaminants. Three commercial epoxy resins were cured using four different alkyl amines. For each resin-amine combination, three levels of amine were used, corresponding to 1/3, 2/3, and all of the amine required to react with the oxirane groups of the resin. The solubility parameters of the 36 resulting model compounds were determined in poorly and moderately hydrogen-bonded solvents. No strongly hydrogen-bonded solvents caused dissolution or swelling. The tolerance of cured resins is discussed in terms of polymer structure.

Rheineck, A. E.↗
NASA NTRS1972

Concerning the production of free radicals in proteins by ultraviolet light.

The response to UV light of several solid proteins and model compounds has been studied in vacuum and at low temperature, using electron paramagnetic resonance techniques. The results indicate that the details of amino acid composition and sequence, and the tertiary structure of a protein are important in determining both the rate of, and the mechanism for, the production of free radicals, and in determining the conditions under which sulfur-type radicals can be produced. The results presented are related to enzyme inactivation and to the UV stability of proteins generally.

Androes, G. M.↗
NASA NTRS1973

Processable high temperature resistant addition type polyimide laminating resins

Basic studies that were performed using model compounds to elucidate the polymerization mechanism of the so-called addition-type (A-type) polyimides are reviewed. The fabrication and properties of polyimide/graphite fiber composites using A-type polyimide prepolymers as the matrix are also reviewed. An alternate method for preparing processable A-type polyimides by means of in situ polymerization of monomer reactants (PMR) on the fiber reinforcement is described. The elevated temperature properties of A-type PMR/graphite fiber composites are also presented.

Serafini, T. T.↗
NASA NTRS1972

Thermally stable macromolecules.

Man-made polymers are compared with certain naturally occurring polymers which have long been used at elevated temperatures. The pyrolysis of model compounds is discussed together with aspects of thermogravimetric analysis, torsional braid analysis, and questions of chemical and radiation stability. Some structure-property relationships are examined, giving attention to asbestos, mica, graphite, and diamond. Questions of bond strengths are investigated along with the stability of ladder polymers and some fundamental concepts in the synthesis of aromatic and heteroaromatic polymers. The substances considered include aromatic single-strand polymers, heteroaromatic polymers, polymers obtained by addition polymerizations, and nonhydrogen-containing polymers. Future trends are also explored.

Pezdirtz, G. F.↗
NASA NTRS1973

A review of processable high temperature resistant addition-type laminating resins

An important finding that resulted from research that was conducted to develop improved ablative resins was the discovery of a novel approach to synthesize processable high temperature resistant polymers. Low molecular weight polyimide prepolymers end-capped with norbornene groups were polymerized into thermo-oxidatively stable modified polyimides without the evolution of void producing volatile materials. This paper reviews basic studies that were performed using model compounds to elucidate the polymerization mechanism of the so-called addition-type polyimides. The fabrication and properties of polyimide/graphite fiber composites using A-type polyimide prepolymer as the matrix are described. An alternate method for preparing processable A-type polyimides by means of in situ polymerization of monomeric reactants on the fiber reinforcement is also described. Polyimide/graphite fiber composite performance at elevated temperatures is presented for A-type polyimides.

Serafini, T. T.↗
NASA NTRS1973

A novel imide synthesis via silyl-blocked diamines

Efforts have resulted in the production of some trimethylsilyl-blocked diamines, which have been employed in a novel manner for the synthesis of polyimide model compounds. Three new silicon-containing diamides were prepared by reacting 1 mol of bis-/N, N prime-bis (trimethylsilyl) -4-aminophonyl/-disubstituted silanes with 2 mol of phthalic anhydride, thus establishing the reactivity of fully silylated diamides in imide formation.

Pratt, J. R.↗
NASA NTRS1977

Cross Linking and Degradation Mechanisms in Model Sealant Candidates

Model compounds were investigated as to which type of heterocyclic ring is the most advantageous for curing sealants based on perfluoroalkylether chains. The relative thermal, thermal oxidative, hydrolytic, and fuel stability of potential crosslinks were determined. Specifically substituted materials were synthesized and evaluation of their stabilities in air, inert atmosphere, water, and Jet-A fuel at 235 and 325 C was made. Three heterocyclic ring systems were considered, namely, triazine, 1,2,4- and 1,3,4-oxadiazoles.

Paciorek, K. L.↗
NASA NTRS1979

Photosensitized oxidation of unsaturated polymers

The photosensitized oxidation or singlet oxygenation of unsaturated hydrocarbon polymers and of their model compounds was reviewed. Emphasis was on cis and trans forms of 1,4-polyisoprene, 1,4-polybutadiene and 1,2-poly(1,4-hexadiene), and on 1,4-poly(2,3-dimethyl-1,3-butadiene). The microstructural changes which occur in these polymers on reaction with O2-1 in solution were investigated by infrared H-1 and C-13 NMR spectroscopy. The polymers were shown to yield allylic hydroperoxides with shifted double bonds according to the ene mechanism established for simple olefins. The photosensitized oxidation of the above unsaturated polymer exhibited zero order kinetics, the relative rates paralleling the reactivities of the corresponding simple olefins towards O2-1.

Golub, M. A.↗
NASA NTRS1980

Photosensitized oxidation of unsaturated polymers

A review of the photosensitized oxidation of singlet oxygenation of unsaturated hydrocarbon polymers and of their model compounds is presented. The cis and trans forms of 1,4-polyisoprene, 1,4-polybutadiene and 1,2-poly(1,4-hexadiene) are studied, and their microstructural changes which occur on reaction with (IO2) in solution were investigated by infrared, (H-1) and (C-13) NMR spectroscopy. The polymers yielded allylic hydroperoxides with shifted double bonds according to the 'ene' mechanism of simple olefins. It was shown that single oxygenation of unsaturated polymers is similar to their low molecular weight analogs, and that the differences are due to secondary processes affecting the (IO2)-reacted polymers.

Golub, M. A.↗
NASA NTRS1980

Reduction of intensity variations on the absorbers of ideal flux concentrators

Large nonuniformities occur in the instantaneous distribution of flux on the absorber of an ideal light concentrator when it is illuminated by a point source such as the sun. These nonuniformities may be reduced by texturing the reflecting surface with small distortions. Such distortions will also be effective if used in the primary reflector of a two-stage concentrator. Data on a model compound parabolic concentrator are presented. The suitability of such concentrators for use by spacecraft is mentioned.

Greenman, P.↗
NASA NTRS1983

High performance liquid chromatographic hydrocarbon group-type analyses of mid-distillates employing fuel-derived fractions as standards

Two high performance liquid chromatographic (HPLC) methods have been developed for the determination of saturates, olefins and aromatics in petroleum and shale derived mid-distillate fuels. In one method the fuel to be analyzed is reacted with sulfuric acid, to remove a substantial portion of the aromatics, which provides a reacted fuel fraction for use in group type quantitation. The second involves the removal of a substantial portion of the saturates fraction from the HPLC system to permit the determination of olefin concentrations as low as 0.3 volume percent, and to improve the accuracy and precision of olefins determinations. Each method was evaluated using model compound mixtures and real fuel samples.

Seng, G. T.↗
NASA NTRS1984

Electron spin resonance study of thermal instability reactions in jet fuels

Free radicals were studied by electron spin resonance (ESR) using model compounds that are representative of constituents of jet fuels. Radical formation was initiated with peroxides and hydroperoxides by using UV photolysis at and near room temperature and thermal initiation at higher temperatures. Both oxygen free and air saturated systems were studied. N-Dodecane was frequently used as a solvent, and a mixture of n-dodecyl radicals was made with a peroxide initiator in n-dodecane (free of oxygen) thermally at 212 C and photolytically at room temperature. Hydrogen abstraction from the 3,4,5 and 6-positions gives radicals that are sufficiently alike that their spectra are essentially superimposed. The radical formed by abstract of hydrogen from the 2-position gives a different spectrum. ESR parameters for these radicals were measured. The radical formed by abstraction of a primary hydrogen was not observed. Similar radicals are formed from n-decane. A variety of exploratory experiments were carried out with systems that give free radical spectra to which was added small amounts of 2,5-dimethylpyrrole.

Zeldes, H.↗