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At least 19 records

X-ray photoelectron spectroscopy study of catalyzed aluminum carbide formation at aluminum-carbon interfaces

Aluminum carbide may form at aluminum-graphite interfaces during the high-temperature processing of graphite fiber-reinforced aluminum metal matrix composites. The chemical interactions leading to the formation of the aluminum carbide in the solid state involve the breaking of the carbon-carbon bonds within the graphite, the transport of the carbon atoms across the interface, and the reaction with the aluminum to form Al4C3. The aluminum carbide formation process has been followed using X-ray photoelectron spectroscopy of model, thin-film, reaction couples. The overall reaction is shown to be catalyzed by the presence of water vapor. Water at the interface increases reaction kinetics by apparently weakening the bonds between the surface carbon atoms and their substrate. This result is in general agreement with what is known to occur during the oxidation of graphite in air.

Rabenberg, L.

On the Stereoselective Synthesis of (+)-Pinoresinol in Forsythia Suspensa from its Achiral Precursor, Coniferyl Alcohol

The residue from Forsythia suspensa stems, upon removal of soluble enzymes, has provided the first evidence for a stereoselective coupling enzyme in lignan biosynthesis. This preparation catalyses the preferred formation (ca 65%) of (+)-[8,8'- C-14] pinoresinol from [8-C-14]coniferyl alcohol in the absence of exogenously provided cofactors; addition of H2O2 had little effect on enantiomeric composition. However, when NAD and malate were supplied, the stereoselectivity of the coupling reaction was significantly enhanced and pinoresinol consisting of ca 80% of the (+)-antipode was obtained. Clearly, the insoluble residue contains a specific coupling enzyme which catalyses (+)-pinoresinol formation from coniferyl alcohol. By contrast, when [8- C-14] sinapyl alcohol was employed as substrate, only racemic syringaresinols were formed: this non-stereoselective peroxidase-catalysed coupling reaction presumably accounts for the low levels of (-)-pinoresinol encountered in this system when coniferyl alcohol is used as a substrate.

Davin, Laurence B.

Synthesis of asymmetric tetracarboxylic acids and corresponding dianhydrides

This invention relates to processes for preparing asymmetrical biphenyl tetracarboxylic acids and the corresponding asymmetrical dianhydrides, namely 2,3,3',4'-biphenyl dianhydride (a-BPDA), 2,3,3',4'-benzophenone dianhydride (a-BTDA) and 3,4'-methylenediphthalic anhydride (-MDPA). By cross-coupling reactions of reactive metal substituted o-xylenes or by cross-coupling o-xylene derivatives in the presence of catalysts, this invention specifically produces asymmetrical biphenyl intermediates that are subsequently oxidized or hydrolyzed and oxidized to provide asymmetric biphenyl tetracarboxylic acids in comparatively high yields. These asymmetrical biphenyl tetracarboxylic acids are subsequently converted to the corresponding asymmetrical dianhydrides without contamination by symmetrical biphenyl dianhydrides.

Chuang, Chun-Hua

Stratospheric chemistry

Recent improvements in the data base for the currently identified reactions describing the chemistry of the major families of trace gas species, HO(x), NO(x), ClO(x), and hydrocarbons are assessed. The important coupling reactions between the families are introduced progressively. Chemical aspects such as heterogeneous reactions and reactions of sodium species, the importance of which are not yet completely established, are discussed. Recent attempts to reconcile some of the more unexpected kinetic behavior which has emerged from the extensive experimental studies of key reactions with current reaction rate theory are also examined. The uncertainties in the current kinetic and photochemical data base is given. The prospects for improvement of data for known reactions of atmospheric importance as well as for the identification of gaps in the chemical description of the atmosphere.

Cox, R. A.

Towards the specification of consecutive steps in macromolecular lignin assembly

When Pinus taeda cell suspension cultures are exposed to 8% sucrose solution, the cells undergo significant intracellular disruption, irregular wall thickening/lignification with concomitant formation of an 'extracellular lignin precipitate. However, addition of potassium iodide (KI), an H202 scavenger, inhibits this lignification response, while the ability to synthesize the monolignols, p-coumaryl and coniferyl alcohols, is retained. Lignin synthesis (i.e. polymerization) is thus temporarily correlated with H202 generation, strongly implying a regulatory role for the latter. Time course analyses of extracellular metabolites leading up to polymer formation reveal that coniferyl alcohol, but not p-coumaryl alcohol, undergoes substantial coupling reactions to give various lignans. Of these, the metabolites, dihydrodehydrodiconiferyl alcohol, shonanin (divanillyl tetrahydrofuran) and its apparent aryl tetralin derivative, cannot be explained simply on the basis of phenolic coupling. It is proposed that these moieties are the precursors of so-called reduced substructures in the lignin macromolecule. This adds a new perspective to the lignin assembly mechanism.

Non-NASA Center

The 1988 Arctic Survey, Diurnal Study (Sunrise and Sunset) and Peak Altitude (22 km) Flights for the In Situ Detection of ClO and BrO from the NASA ER-2 Aircraft

Two critical areas of research were addressed successfully by this research. The first involves NASA ER-2 airborne observations of ClO and BrO radical destruction of ozone within the arctic vortex. The second involves the analysis of diurnal variations in ClO, to test the production and loss rates of ClO that constitutes the test for coupling reactions between the chlorine and nitrogen systems. We discuss results from this research in order.

Anderson, James G.

Solubility of HOBr in Acidic Solution and Implications for Liberation of Halogens Via Aerosol Processing

Halogen species are known to catalytically destroy ozone in several regions of the atmosphere. In addition to direct catalytic losses, bromine compounds can indirectly enhance ozone loss through coupling to other radical families. Hypobromous acid (HOBr) is a key species in the linkage of BrOx to ClOx and HOx. The aqueous- phase coupling reaction HOBr + HCI (right arrow) BrCl + H2O may provide a pathway for chlorine activation on sulfate aerosols at temperatures warmer than those required for polar stratospheric cloud formation. We have measured t h e solubility of HOBr in 45 - 70 wt% sulfuric acid solutions. Over the temperature range 201 - 252 K, HOBr is quite soluble in sulfuric acid, H* = 10(exp 4) - 10(exp 7) mol dm(exp -3) atm(exp -1). The expected inverse dependence of H* on temperature was observed, but only a weak dependence on acidity was found. The solubility of HOBr is comparable to that of HBr, indicating that equilibrium concentrations of HOBr could equal or exceed those of HBr in upper tropospheric and lower stratospheric aerosols. Despite the high solubility of HOBr, aerosol volumes are not large enough to sequester a significant fraction of inorganic bromine from the gas phase. Our measurements of HOBr uptake in aqueous sulfuric acid in the presence of other brominated gases show the evolution of gaseous products including Br2O and Br2.

Iraci, Laura T.

Synthesis and Photoluminescent Properties of Arylethynyl substituted 9,10-Anthraquinones

A series of arylethynyl substituted anthraquinones were synthesized via Sonogashira coupling reactions of 2,7- dibromo-, 2,6-dibromo- and 2-bromoanthraquinone with para-substituted phenylacetylenes. While the redox properties of those compounds are almost insensitive to substitution, their absorption maxima are linearly related to the Hammett constants for electron donating and electron withdrawing groups separately. All compounds are photoluminescent both in solution (quantum yield of emission approximately 2%) and as solids. X-ray crystallographic characterization of 2,7-bisphenylethynyl anthraquinone indicates a monoclinic p2(l/n) space group and no indication for pi-overlap that would promote self-quenching. The emission maxima are red- shifted by both electron donating and electron withdrawing groups alike. The Stokes shifts of all compounds are significant and are correlated to the electronic properties of the substituents. The reduced forms of these compounds are also photoluminescent and the emission originates from the dihydroanthraquinone core.

Yang, Jin-Hua

Arylethynyl Substituted 9,lO-Anthraquinones: Tunable Stokes Shifts by Substitution and Solvent Polarity

2-Arylethynyl- and 2,6- and 2,7-diarylethynyl-substituted 9,lO-anthraquinones were synthesized via Sonogashira coupling reactions of 2-bromo-, 2,6-dibromo-, and 2,7-dibromo-9,10- anthraquinone with para-substituted phenylacetylenes. While the redox properties of those compounds are almost insensitive to substitution, their absorption maxima are linearly related to the Hammett constants with different slopes for electron donors and electron acceptors. ABI compounds are photoluminescent both in solution (quantum yields of emission <= 6 %), and as solids. The emission spectra have the characteristics of charge-transfer bands with large Stokes shifts (100-250 nm). The charge-transfer character of the emitting state is supported by large dipole moment differences between the ground and the excited state as concluded on the basis of molecular modeling and Lippert-Mataga correlations of the Stokes shifts with solvent polarity. Maximum Stokes shifts are attained by both electron-donating and -withdrawing groups. This is explained by a destabilization of the HOMO by electron donors and a stabilization of the LUMO by electron acceptors. X-ray crystallographic analysis of, for example, 2,7-bisphenylethynfl- 9,lO-anthraquinone reveals a monoclinic P21In space group and no indication for pi-overlap that would promote quenching, thus explaining emission from the solid state. Representative reduced forms of the title compounds were isolated as stable acetates of the corresponding dihydrs-9,10- anthraquinones. The emission of these compounds is blue-shifted relative to the parent oxidized forms and is attributed to internal transitions in the dihydro-9,lO-anthraquinone core.

Yang, Jinhua

Synthesis and Characterization of Ru(II) Tris(1,1O-phenanthroline)-Electron Acceptor Dyads Incorporating the 4-benzoyl-N-methylpyridinium Cation or N-Benzyl-N'-methyl-viologen. Improving the Dynamic Range, Sensitivity and Response Time of Sol-Gel Based Optical Oxygen Sensors

The title compounds (1 and 2, above) were synthesized by Sonogashira coupling reactions of appropriate Ru(1I) complexes with the electron a cceptors. Characterization was conducted in solution and in frozen ma trices. Finally, the title compounds were evaluated as dopants of sol-gel materials. It was found that the intramolecular quenching efficie ncy of 4-benzoyl-Nmethylpyridinium cation in solution depends on the solvent: photoluminescence is quenched completely in CH,CN, but not i n methanol or ethanol. On the other hand, intramolecular emission que nching by 4-benzyl-N-methyl viologen is complete in all solvents. The difference between the two quenchers is traced electrochemically to t he solvation of the 4-benzoyl-Nmethylpyridiniums by alcohol. In froze n matrices or adsorbed on the surfaces of silica aerogel, both Ru(I1) complex/electron acceptor dyads of this study are photoluminescent, and the absence of quenching has been traced to the environmental rigi dity. When doped aerogels are cooled at 77 K, the emission intensity increases by approximately 4x, and the spectra shift to the blue, analogous to what is observed with Ru(I1) complexes in solutions undergoi ng fluid-to-rigid transition. However, in contrast to frozen solution s, the luminescent moieties in the bulk of aerogels kept at low tempe ratures are still accessible to gas-phase quenchers diffusing through the mesopores, leading to more sensitive platforms for sensors than o ther room-temperature configurations. Thus the photoluminescence of o ur Ru(I1) complex dyads adsorbed on aerogel is quenchable by O2 both at room temperature and at 77 K. Furthermore, it was also found that O 2 modulates the photoluminescence of aerogels doped with 4-benzoyl -N -methylpyridinium-based dyads over a wider dynamic range compared wi th aerogels doped with either our vislogen-based dyads or with Ru(I1) tris(1,lO-phenanthroline) itself.

Leventis, Nicholas

Effects of Material Degradation on the Structural Integrity of Composite Materials: Experimental Investigation and Modeling of High Temperature Degradation Mechanisms

It has previously been demonstrated that simple coupled reaction-diffusion models can approximate the aging behavior of PMR-15 resin subjected to different oxidative environments. Based on empirically observed phenomena, a model coupling chemical reactions, both thermal and oxidative, with diffusion of oxygen into the material bulk should allow simulation of the aging process. Through preliminary modeling techniques such as this it has become apparent that accurate analytical models cannot be created until the phenomena which cause the aging of these materials are quantified. An experimental program is currently underway to quantify all of the reaction/diffusion related mechanisms involved. The following contains a summary of the experimental data which has been collected through thermogravimetric analyses of neat PMR-15 resin, along with analytical predictions from models based on the empirical data. Thermogravimetric analyses were carried out in a number of different environments - nitrogen, air and oxygen. The nitrogen provides data for the purely thermal degradation mechanisms while those in air provide data for the coupled oxidative-thermal process. The intent here is to effectively subtract the nitrogen atmosphere data (assumed to represent only thermal reactions) from the air and oxygen atmosphere data to back-figure the purely oxidative reactions. Once purely oxidative (concentration dependent) reactions have been quantified it should then be possible to quantify the diffusion of oxygen into the material bulk.

Cunningham, Ronan A.

Chemical kinetic models for combustion of hydrocarbons and formation of nitric oxide

The formation of nitrogen oxides NOx during combustion of methane, propane, and a jet fuel, JP-4, was investigated in a jet stirred combustor. The results of the experiments were interpreted using reaction models in which the nitric oxide (NO) forming reactions were coupled to the appropriate hydrocarbon combustion reaction mechanisms. Comparison between the experimental data and the model predictions reveals that the CH + N2 reaction process has a significant effect on NO formation especially in stoichiometric and fuel rich mixtures. Reaction models were assembled that predicted nitric oxide levels that were in reasonable agreement with the jet stirred combustor data and with data obtained from a high pressure (5.9 atm (0.6 MPa)), prevaporized, premixed, flame tube type combustor. The results also suggested that the behavior of hydrocarbon mixtures, like JP-4, may not be significantly different from that of pure hydrocarbons. Application of the propane combustion and nitric oxide formation model to the analysis of NOx emission data reported for various aircraft gas turbines showed the contribution of the various nitric oxide forming processes to the total NOx formed.

Jachimowski, C. J.

Exhaust Nozzle for a Multitube Detonative Combustion Engine

An improved type of exhaust nozzle has been invented to help optimize the performances of multitube detonative combustion engines. The invention is applicable to both air-breathing and rocket engines used to propel some aircraft and spacecraft, respectively. In a detonative combustion engine, thrust is generated through the expulsion of combustion products from a detonation process in which combustion takes place in a reaction zone coupled to a shock wave. The combustion releases energy to sustain the shock wave, while the shock wave enhances the combustion in the reaction zone. The coupled shockwave/reaction zone, commonly referred to as a detonation, propagates through the reactants at very high speed . typically of the order of several thousands of feet per second (of the order of 1 km/s). The very high speed of the detonation forces combustion to occur very rapidly, thereby contributing to high thermodynamic efficiency. A detonative combustion engine of the type to which the present invention applies includes multiple parallel cylindrical combustion tubes, each closed at the front end and open at the rear end. Each tube is filled with a fuel/oxidizer mixture, and then a detonation wave is initiated at the closed end. The wave propagates rapidly through the fuel/oxidizer mixture, producing very high pressure due to the rapid combustion. The high pressure acting on the closed end of the tube contributes to forward thrust. When the detonation wave reaches the open end of the tube, it produces a blast wave, behind which the high-pressure combustion products are expelled from the tube. The process of filling each combustion tube with a detonable fuel/oxidizer mixture and then producing a detonation repeated rapidly to obtain repeated pulses of thrust. Moreover, the multiple combustion tubes are filled and fired in a repeating sequence. Hence, the pressure at the outlet of each combustion tube varies cyclically. A nozzle of the present invention channels the expansion of the pulsed combustion gases from the multiple combustion tubes into a common exhaust stream, in such a manner as to enhance performance in two ways: (1) It reduces the cyclic variations of pressure at the outlets of the combustion tubes so as to keep the pressure approximately constant near the optimum level needed for filling the tubes, regardless of atmospheric pressure at the altitude of operation; and (2) It maximizes the transfer of momentum from the exhaust gas to the engine, thereby maximizing thrust. The figure depicts a typical engine equipped with a nozzle according to the invention. The nozzle includes an interface section comprising multiple intake ports that couple the outlets of the combustion tubes to a common plenum. Proceeding from its upstream to its downstream end, the interface section tapers to a larger cross-sectional area for flow. This taper fosters expansion of the exhaust gases flowing from the outlets of the combustion tubes and contributes to the desired equalization of exhaust combustion pressure. The cross-sectional area for flow in the common plenum is greater than, or at least equal to, the combined cross-sectional flow areas of the combustor tubes. In the common plenum, the exhaust streams from the individual combustion tubes mix to form a single compound subsonic exhaust stream. Downstream of the common plenum is the throat that tapers to a smaller flow cross section. In this throat, the exhaust gases become compressed to form a compound sonic gas stream. Downstream of the throat is an expansion section, which typically has a bell or a conical shape. (The expansion section can be truncated or even eliminated in the case of an air-breathing engine.) After entering the expansion section, the exhaust gases expand rapidly from compound sonic to compound supersonic speeds and are then vented to the environment. The basic invention admits of numerous variations. For example, the combustion tubes can be arranged around the central axin a symmetrical or asymmetrical pattern other than the one shown in the figure. For another example, the flow cross-sectional area(s) of one or more of the intake ports in the interface section, of the common plenum, the throat, and/or the expansion section can be varied, either symmetrically or asymmetrically, to adjust dynamics of the exhaust stream or to direct the thrust vector away from the central axis.

Bratkovich, Thomas E.

A study of heavy-heavy nuclear reactions

A simplified theory for heavy ion scattering shows good agreement with heavy ion absorption experiments. Theoretical implications on the complete coupled channel reaction equations are discussed.

Khandelwal, G. S.

Chemical Constraints Governing the Origin of Metabolism: The Thermodynamic Landscape of Carbon Group Transformations

The thermodynamics of organic chemistry under mild aqueous conditions was examined in order to begin to understand its influence on the structure and operation of metabolism and its antecedents. Free energies were estimated for four types reactions of biochemical importance carbon-carbon bond cleavage and synthesis, hydrogen transfer between carbon groups, dehydration of alcohol groups, and aldo-keto isomerization. The energies were calculated for mainly aliphatic groups composed of carbon, hydrogen, and oxygen. The energy values showed that (1) when carbon-carbon bond cleavage involves two different types of functional groups, transfer of the shared electron-pair to the more reduced carbon group is energetically favored over transfer to the more oxidized carbon group, and (2) the energy of carbon-carbon bond transformation is strongly dependent on the type of functional group that donates the shared electron-pair during cleavage, and the group that accepts the shared electron-pair during synthesis, and (3) the energetics of C-C bond transformation is determined primarily by the half-reaction energies of the couples: carbonyl/carboxylic acid, carboxylic acid/carbon dioxide, alcohol/carbonyl, and hydrocarbon/alcohol. The energy of hydrogen-transfer between carbon groups was found to depend on the functional group class of both the hydrogen-donor and hydrogen-acceptor. From these and other observations we concluded that the chemistry of the origin of metabolism (and to a lesser degree modem metabolism) is strongly constrained by the (1) limited disproportionation energy of organic substrates that can be dissipated in a few irreversible reactions, (2) the energy-dominance of few half-reaction couples in carbon-carbon bond transformation that establishes whether a chemical reaction is energetically irreversible, reversible or unfeasible, and (3) the dependence of the transformation-energy on the oxidation state of carbon groups (functional group type) which is contingent on prior reactions in the synthetic pathway.

Weber, Arthur L.

Minimum-Time and Vibration Avoidance Attitude Maneuver for Spacecraft with Torque and Momentum Limit Constraints in Redundant Reaction Wheel Configuration

In this paper, we present an optimal open-loop slew trajectory algorithm developed at GSFC for the so-called "Yardstick design" of the James Webb Space Telescope (JWST). JWST is an orbiting infrared observatory featuring a lightweight, segmented primary mirror approximately 6 meters in diameter and a sunshield approximately the size of a tennis court. This large, flexible structure will have significant number of lightly damped, dominant flexible modes. With very stringent requirements on pointing accuracy and image quality, it is important that slewing be done within the required time constraint and with minimal induced vibration in order to maximize observing efficiency. With reaction wheels as control actuators, initial wheel speeds as well as individual wheel torque and momentum limits become dominant constraints in slew performance. These constraints must be taken into account when performing slews to ensure that unexpected reaction wheel saturation does not occur, since such saturation leads to control failure in accurately tracking commanded motion and produces high frequency torque components capable of exciting structural modes. A minimum-time constraint is also included and coupled with reaction wheel limit constraints in the optimization to minimize both the effect of the control torque on the flexible body motion and the maneuver time. The optimization is on slew command parameters, such as maximum slew velocity and acceleration, for a given redundant reaction wheel configuration and is based on the dynamic interaction between the spacecraft and reaction wheel motion. Analytical development of the slew algorithm to generate desired slew position, rate, and acceleration profiles to command a feedback/feed forward control system is described. High-fidelity simulation and experimental results are presented to show that the developed slew law achieves the objectives.

Ha, Kong Q.

Comparison of vibration dissociation coupling and radiative heat transfer models for AOTV/AFE flowfields

A series of detailed studies comparing various vibration dissociation coupling models, reaction systems and rates, and radiative heating models has been conducted for the nonequilibrium stagnation region of an AFE/AOTV vehicle. Atomic and molecular nonequilibrium radiation correction factors have been developed and applied to various absorption coefficient step models, and a modified vibration dissociation coupling model has been shown to yield good vibration/electronic temperature and concentration profiles. While results indicate sensitivity to the choice of vibration dissociation coupling model and to the nitrogen electron impact ionization rate, by proper combinations accurate flowfield and radiative heating results can be obtained. These results indicate that nonequilibrium effects significantly affect the flowfield and the radiative heat transfer. However, additional work is needed in ionization chemistry and absorption coefficient modeling.

Carlson, Leland A.

Iron catalyst chemistry in modeling a high-pressure carbon monoxide nanotube reactor

The high-pressure carbon monoxide (HiPco) technique for producing single-wall carbon nanotubes (SWNTs) is analyzed with the use of a chemical reaction model coupled with flow properties calculated along streamlines, calculated by the FLUENT code for pure carbon monoxide. Cold iron pentacarbonyl, diluted in CO at about 30 atmospheres, is injected into a conical mixing zone, where hot CO is also introduced via three jets at 30 degrees with respect to the axis. Hot CO decomposes the Fe(CO)5 to release atomic Fe. Then iron nucleates and forms clusters that catalyze the formation of SWNTs by a disproportionation reaction (Boudouard) of CO on Fe-containing clusters. Alternative nucleation rates are estimated from the theory of hard sphere collision dynamics with an activation energy barrier. The rate coefficient for carbon nanotube growth is estimated from activation energies in the literature. The calculated growth was found be about an order of magnitude greater than measured, regardless of the nucleation rate. A study of cluster formation in an incubation zone prior to injection into the reactor shows that direct dimer formation from Fe atoms is not as important as formation via an exchange reaction of Fe with CO in FeCO.

Evaluation Studies