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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.

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.

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.

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.

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.

Numerical simulation of shock-induced combustion/detonation

A numerical study is conducted to simulate the shock-induced combustion in premixed H2-air mixtures. Two types of bodies, blunt (spherical projectile) and sharp (wedge), are considered in the study. A nine-species, 18-step finite-rate H2-air chemical reaction mechanism coupled with the Navier-Stokes equations is solved. The flow field over the blunt body is found to be unsteady, when the projectile velocity is same as the Chapman-Jouget velocity of the mixture. The unsteadiness is caused by the periodic instabilities originating in the stagnation zone. Numerical results show good qualitative agreement with the ballistic range shadowgraph. In addition, the frequency of oscillations, determined by using the Fourier power spectrum, is found to be in good agreement with the experiment. The flow field over the wedge is found to be stable for the conditions considered in this study. The oblique detonation wave structure is investigated and the important flow features are discussed.

Singh, D. J.

High-Altitude Aircraft and Balloon-Borne Observations of OH, HO2, ClO, BrO, NO2, ClONO2, ClOOCl, H2O, and O3 in Earth's Stratosphere

Using observations from balloon-borne instruments and aircraft-borne instruments the investigation arrived at the following developments.: (1) Determination of the dominant catalytic cycles that destroy ozone in the lower stratosphere; (2) The partial derivatives of the rate limiting steps are observables in the lower stratosphere; (3) Recognition that the "Low NOx" condition is the regime that holds the greatest potential for misjudgement of Ozone loss rates; (4) Mapping of the Bromine radical contribution to the ozone destruction rate in the lower stratosphere; (5) Observation of OH, HO2 and ClO in the plume of the Concorde SST in the stratosphere; (6) Determination of the diurnal behavior of OH in the lower stratosphere; (7) Observed OH and H02 in the Troposphere and the interrelationship between Ozone and OH, HO2, CO and NO; (8) Analysis of the Catalytic Production of Ozone and Reactions that Couple OH and H02 in the Troposphere; (9) The continuing development of the understanding of the Tropopause temperatures, water vapor mixing ratios, and vertical advection and the mixing in of mid-latitude air; (10) Performed Multiple Tracer Analyses as a diagnostic of water vapor intrusion into the "Middle World" (i.e., the lowermost stratsophere); (11) Flight testing of a new instrument for the In Situ detection of ClON02 from the ER-2; (12) Laser induced fluorescence detection of NO2. There is included an in depth discussion of each of these developments and observations.

Anderson, James G.

Transport of Light Ions in Matter

A recent set of light ion experiments are analyzed using the Green's function method of solving the Boltzmann equation for ions of high charge and energy (the GRNTRN transport code) and the NUCFRG2 fragmentation database generator code. Although the NUCFRG2 code reasonably represents the fragmentation of heavy ions, the effects of light ion fragmentation requires a more detailed nuclear model including shell structure and short range correlations appearing as tightly bound clusters in the light ion nucleus. The most recent NTJCFRG2 code is augmented with a quasielastic alpha knockout model and semiempirical adjustments (up to 30 percent in charge removal) in the fragmentation process allowing reasonable agreement with the experiments to be obtained. A final resolution of the appropriate cross sections must await the full development of a coupled channel reaction model in which shell structure and clustering can be accurately evaluated.

Wilson, J. W.

Organic chemistry on Titan

Observations of nonequilibrium phenomena on the Saturn satellite Titan indicate the occurrence of organic chemical evolution. Greenhouse and thermal inversion models of Titan's atmosphere provide environmental constraints within which various pathways for organic chemical synthesis are assessed. Experimental results and theoretical modeling studies suggest that the organic chemistry of the satellite may be dominated by two atmospheric processes: energetic-particle bombardment and photochemistry. Reactions initiated in various levels of the atmosphere by cosmic ray, Saturn wind, and solar wind particle bombardment of a CH4 - N2 atmospheric mixture can account for the C2-hydrocarbons, the UV-visible-absorbing stratospheric haze, and the reddish color of the satellite. Photochemical reactions of CH4 can also account for the presence of C2-hydrocarbons. In the lower Titan atmosphere, photochemical processes will be important if surface temperatures are sufficiently high for gaseous NH3 to exist. Hot H-atom reactions initiated by photo-dissociation of NH3 can couple the chemical reactions of NH3 and CH4 and produce organic matter.

Chang, S.

Oxidative acylation using thioacids

Several important prebiotic reactions, including the coupling of amino acids into polypeptides by the formation of amide linkages, involve acylation. Theae reactions present a challenge to the understanding of prebiotic synthesis. Condensation reactions relying on dehydrating agents are either inefficient in aqueous solution or require strongly acidic conditions and high temperatures. Activated amino acids such as thioester derivatives have therefore been suggested as likely substrates for prebiotic peptide synthesis. Here we propose a closely related route to amide bond formation involving oxidative acylation by thioacids. We find that phenylalanine, leucine and phenylphosphate are acylated efficiently in aqueous solution by thioacetic acid and an oxidizing agent. From a prebiotic point of view, oxidative acylation has the advantage of proceeding efficiently in solution and under mild conditions. We anticipate that oxidative acylation should prove to be a general method for activating carboxylic acids, including amino acids.

Non-NASA Center

Reaction control system plume flow field interaction effects on the Space Shuttle orbiter

This paper presents an analysis of data obtained from wind tunnel tests of the aerodynamic interference induced by the reaction control system jets on Space Shuttle orbiter configurations. The test data was obtained using cold gas simulation techniques with nozzles scaled to match jet exit momentum ratio as the primary parameter at Mach numbers from 2.5 to 10. Significant induced effects have been found that degrade the performance of the pitch and roll reaction controls and that induce cross-coupling effects for yaw reaction control. Analysis of the induced data shows good correlation with jet exit momentum ratio.

Rausch, J. R.

Excitable dynamics in high-Lewis number premixed gas combustion at normal and microgravity

Freely-propagating, premixed gas flames in high-Lewis (Le) number, quiescent mixtures are studied experimentally in tubes of various diameter at normal (lg) and microgravity (mu g). A premixture of lean butane and oxygen diluted with helium, argon, neon, nitrogen or a mixture of multiple diluents is examined such that the thermal diffusivity of the mixture (and to a lesser extent, the mass diffusivity of the rate-limiting component) is systematically varied. In effect, different diluents allow variation of the Le without changing the chemistry. The flames are recorded with high speed cinematography and their stability is visually assessed. Different modes of propagation were observed depending on the diameter of the tubes (different conductive heat loss), the composition of the mixture and the g-level. At 1g, four modes of propagation were observed in small and intermediate diameter tubes (large conductive heat loss): (1) steadily propagating flames, (2) radial and longitudinal pulsating flames, (3) 'wavering' flames, and (4) rotating spiral flames. As the diameter of the tube increases, the radial modes become more pronounced while the longitudinal modes systematically disappear. Also, multiple, simultaneous, spatially-separated 'pacemaker' sites are observed in intermediate and large diameter tubes. Each site starts as a small region of high luminosity and develops into a flamelet which assumes the form of one of the fore mentioned modes. These flamelets eventually interact, annihilate each other in their regions of intersection and merge at their newly created free-ends. For very large tubes, radially-propagating wave-trains (believed to be 'trigger waves') are observed. These are analogous to the radial pulsations observed in the smaller diameter tubes. At mu g, three modes of propagation have been observed: (1) steadily propagating flames, (2) radial and longitudinal pulsating flames, and (3) multi-armed, rotating flames. Since the pulsating mode exists at mu g and 1g, buoyant flicker is not the mechanism which drives the pulsations. Moreover, all of the instabilities at 1g and mu g have characteristic frequencies on the O(100Hz). This value is lower than the fundamental, longitudinal acoustic frequencies of the tubes which suggests that the instabilities are not acoustically driven. The patterns formed by this reaction bear remarkable similarities with the patterns formed in most excitable media when the behavior of the system is driven by couplings between chemical reaction and diffusion (e.g., Belousov-Zhabotinsky reaction, Patterns in slime molds, spiral waves in the retina of a bird's eye). While it is recognized that the chemical mechanism associated with this premixed gas reaction is exponentially sensitive to temperature and undoubtedly different from those which govern previously observed excitable media (most are isothermal, or weakly exothermic, liquid phase reactions), similar spatial and temporal patterns should not come as a complete surprise considering heat and mass diffusion are self similar. It is concluded that this premixed gas system is a definitive example of a diffusive-thermal, gas-phase oscillator based on these experimental results and their favorable comparison with theory.

Pearlman, Howard

Statistical modeling of capture, association, and exit-channel dynamics in the CH3(+)/CH3CN system

The ion-molecule CH3(+) + CH3CN reaction is presently modeled by means of a master equation treatment incorporating weak collisions. The parameter required for the Rice-Ramsberger-Kassel-Markus (RRKM) treatment is derived from an ab initio investigation of the energy surface in question, and a means of including the capture rate coefficients in the RRKM approach is developed in which only the hindered dipole rotation is coupled in the reaction coordinate at large separations. Unimolecular rate coefficients for the (CH3CNCH3+)-activated complex are calculated for all product channels in the 300-600 K temperature range.

Smith, S. C.

An efficient, explicit finite-rate algorithm to compute flows in chemical nonequilibrium

An explicit finite-rate code was developed to compute hypersonic viscous chemically reacting flows about three-dimensional bodies. Equations describing the finite-rate chemical reactions were fully coupled to the gas dynamic equations using a new coupling technique. The new technique maintains stability in the explicit finite-rate formulation while permitting relatively large global time steps.

Palmer, Grant