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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 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
NASA NTRS1990

Localized basis functions and other computational improvements in variational nonorthogonal basis function methods for quantum mechanical scattering problems involving chemical reactions

The Generalized Newton Variational Principle for 3D quantum mechanical reactive scattering is briefly reviewed. Then three techniques are described which improve the efficiency of the computations. First, the fact that the Hamiltonian is Hermitian is used to reduce the number of integrals computed, and then the properties of localized basis functions are exploited in order to eliminate redundant work in the integral evaluation. A new type of localized basis function with desirable properties is suggested. It is shown how partitioned matrices can be used with localized basis functions to reduce the amount of work required to handle the complex boundary conditions. The new techniques do not introduce any approximations into the calculations, so they may be used to obtain converged solutions of the Schroedinger equation.

Schwenke, David W.↗
NASA NTRS1980

The effect of preparation conditions on the structure and mechanical properties of reaction-sintered silicon nitride

The microstructure of reaction sintered silicon nitride (RSSN) was changed over a wide range by varying the grain density, grain size of the silicon starting powder, nitriding conditions, and by introducing artificial pores. The influence of single microstructural parameters on mechanical properties like room temperature strength, creep behavior, and resistance to thermal shock was investigated. The essential factors influencing these properties were found to be total porosity, pore size distribution, and the fractions of alpha and beta Si3N4. In view of high temperature engineering applications of RSSN, potentials for optimizing the material's properties by controlled processing are discussed.

Heinrich, J.↗
NASA NTRS1997

Structure of an anti-HIV-1 hammerhead ribozyme complex with a 17-mer DNA substrate analog of HIV-1 gag RNA and a mechanism for the cleavage reaction: 750 MHz NMR and computer experiments

The structure of an anti-HIV-1 ribozyme-DNA abortive substrate complex was investigated by 750 MHz NMR and computer modeling experiments. The ribozyme was a chimeric molecule with 30 residues-18 DNA nucleotides, and 12 RNA residues in the conserved core. The DNA substrate analog had 17 residues. The chimeric ribozyme and the DNA substrate formed a shortened ribozyme-abortive substrate complex of 47 nucleotides with two DNA stems (stems I and III) and a loop consisting of the conserved core residues. Circular dichroism spectra showed that the DNA stems assume A-family conformation at the NMR concentration and a temperature of 15 degrees C, contrary to the conventional wisdom that DNA duplexes in aqueous solution populate entirely in the B-form. It is proposed that the A-family RNA residues at the core expand the A-family initiated at the core into the DNA stems because of the large free energy requirement for the formation of A/B junctions. Assignments of the base H8/H6 protons and H1' of the 47 residues were made by a NOESY walk. In addition to the methyl groups of all T's, the imino resonances of stems I and III and AH2's were assigned from appropriate NOESY walks. The extracted NMR data along with available crystallographic data, were used to derive a structural model of the complex. Stems I and III of the final model displayed a remarkable similarity to the A form of DNA; in stem III, a GC base pair was found to be moving into the floor of the minor groove defined by flanking AT pairs; data suggest the formation of a buckled rhombic structure with the adjacent pair; in addition, the base pair at the interface of stem III and the loop region displayed deformed geometry. The loop with the catalytic core, and the immediate region of the stems displayed conformational multiplicity within the NMR time scale. A catalytic mechanism for ribozyme action based on the derived structure, and consistent with biochemical data in the literature, is proposed. The complex between the anti HIV-1 gag ribozyme and its abortive DNA substrate manifests in the detection of a continuous track of A.T base pairs; this suggests that the interaction between the ribozyme and its DNA substrate is stronger than the one observed in the case of the free ribozyme where the bases in stem I and stem III regions interact strongly with the ribozyme core region (Sarma, R. H., et al. FEBS Letters 375, 317-23, 1995). The complex formation provides certain guidelines in the design of suitable therapeutic ribozymes. If the residues in the ribozyme stem regions interact with the conserved core, it may either prevent or interfere with the formation of a catalytically active tertiary structure.

NASA Discipline Exobiology↗
NASA NTRS2002

A methodology for modeling the mechanical interaction between a reaction wheel and a flexible structure

This paper presents a modeling methodology used to predict the performance of a flexible structure, such as a space telescope, in the presence of an on-board vibrational disturbance source, such as a reaction wheel assembly (RWA). Both decoupled and coupled analysis methods are presented. The decoupled method relies on blocked RWA disturbances, measured with the RWA hardmounted to a rigid surface. The coupled method corrects the blocked RWA disturbance boundary conditions using "force filters," which depend on estimates of the interface accelerances of the RWA and space-craft. Both methods were validated on the Micro-Precision Interferometer testbed at the Jet Propulsion Laboratory. Experimental results are encouraging, indicating that both methods provide sufficient accuracy compared to measured values; however, the coupled method provides the best results when the gyroscopic nature of the spinning RWA is captured in the RWA accelerance model. Additionally, the RWA disturbance cross spectral density terms are found to be influential.

vibration↗
NASA NTRS2017

Development of a Detailed Surface Chemistry Framework in DSMC

Many of the current direct simulation Monte Carlo (DSMC) codes still employ only simple surface catalysis models. These include only basic mechanisms such as dissociation, recombination, and exchange reactions, without any provision for adsorption and finite rate kinetics. Incorporating finite rate chemistry at the surface is increasingly becoming a necessity for various applications such as high speed re-entry flows over thermal protection systems (TPS), micro-electro-mechanical systems (MEMS), surface catalysis, etc. In the recent years, relatively few works have examined finite-rate surface reaction modeling using the DSMC method.In this work, a generalized finite-rate surface chemistry framework incorporating a comprehensive list of reaction mechanisms is developed and implemented into the DSMC solver SPARTA. The various mechanisms include adsorption, desorption, Langmuir-Hinshelwood (LH), Eley-Rideal (ER), Collision Induced (CI), condensation, sublimation, etc. The approach is to stochastically model the various competing reactions occurring on a set of active sites. Both gas-surface (e.g., ER, CI) and pure-surface (e.g., LH, desorption) reaction mechanisms are incorporated. The reaction mechanisms could also be catalytic or surface altering based on the participation of the bulk-phase species (e.g., bulk carbon atoms). Marschall and MacLean developed a general formulation in which multiple phases and surface sites are used and we adopt a similar convention in the current work. Microscopic parameters of reaction probabilities (for gas-surface reactions) and frequencies (for pure-surface reactions) that are require for DSMC are computed from the surface properties and macroscopic parameters such as rate constants, sticking coefficients, etc. The energy and angular distributions of the products are decided based on the reaction type and input parameters. Thus, the user has the capability to model various surface reactions via user-specified reaction rate constants, surface properties and parameters.

Gas↗
NASA NTRS1993

Kinetics and Mechanism of the CIO + CIO Reaction: Pressure and Temperature Dependences of the Bimolecular and Termolecular Channels andThermal Decomposition of Chlorine Peroxide, CIOOCI

The kinetics and mechanism of the CIO + CIO reaction and the thermal decomposition of CIOOCI were studied using the flash photolysis/long path ultraviolet absorption technique. Pressure and temperature dependences were determined for the rate coefficients for the bimolecular and termolecular reaction channels, and for the thermal decompositon of CIOOCI.

Kinetics Thermal Decomposition Biomolecul↗
NASA NTRS1994

Fundamental mechanisms in premixed flame propagation via vortex-flame interactions: Numerical simulations

The goal of the present study is to assess numerically the ability of single-step and two-step chemical models to describe the main features encountered during the interaction between a two-dimensional vortex pair and a premixed laminar flame. In the two-step mechanism, the reaction kinetics are represented by a first chain branching reaction A + X yields 2X and a second chain termination reaction X + X yields P. This paper presents the fundamental mechanisms occurring during vortex-flame interactions and the relative impact of the major parameters encountered in turbulent premixed flames and suspected of playing a role in quenching mechanism: (1) Influence of stretch is investigated by analyzing the contribution of curvature and tangential strain on the local structure of the flame. The effect of Lewis number on the flame response to a strained field is analyzed. (2) Radiative heat losses which are suspected to be partially or totally responsible for quenching are also investigated. (3) The effect of the diffusion of the radicals is studied using a two-step mechanism in which an intermediate species is present. The parameters of the two-step mechanism are entirely determined from physical arguments. (4) Precise quantitative comparisons between the DNS and the experimental results of Samaniego et al are performed. These comparisons concern the evolution of the minimum heat release rate found along the flame front during the interaction and the distribution of the heat release rate along the flame front.

Mantel, Thierry↗
NASA NTRS1987

The carbon dioxide chaperon efficiency for the reaction H + O2 + M yields HO2 + M from ignition delay times behind reflected shock waves

Ignition delay times for stoichiometric hydrogen-oxygen in argon with and without carbon dioxide were measured behind reflected shock waves. A 20-reaction kinetic mechanism models the measured hydrogen-oxygen delay times over the temperature range 950 to 1300 K. The chaperon efficiency for carbon dioxide determined for the hydrogen-oxygen carbon dioxide mixture was 7.0. This value is in agreement with literature values but much less than a recent value obtained from flow tube experiments. Delay times measured behind a reflected shock wave were about 20% longer than those measured behind incident shock waves. The kinetic mechanism successfully modeled the high-pressure data of Skinner and the hydrogen-air data of Stack. It is suggested that the lowest temperature points for the hydrogen-air data of Slack are unreliable and that the 0.27-atm data may illustrate a case where vibrational relaxation of nitrogen is important. The reaction pathway HO2 yields H2O2 yields OH yields H was required to model the high-pressure data of Skinner. The successful modeling of the stoichiometric hydrogen-air data demonstrates the appropriateness of deriving kinetic models from data for gas mixtures highly diluted with argon. The technique of reducing a detailed kinetic mechanism to only the important reactions for a limited range of experimental data may render the mechanism useless for other test conditions.

Brabbs, Theodore A.↗
NASA NTRS1986

Effects of test facility contaminants on supersonic hydrogen-air diffusion flames

Results are presented from an analytical assessment of the effects of NO and H2O in air on the ignition and reaction of hydrogen. Three flow models of the burning process were used, each including a 32 reaction chemistry mechanism. These models were a plug flow reactor to determine ignition and reaction times; a well-stirred reactor to assess flame stability or blow-off; and a parabolic Navier-Stokes code to examine the diffusion flame combustion. The diffusion flame was computed for a cold supersonic H2 jet coaxial with a supersonic air stream at a static temperature of 1100 K and a pressure of 1 atmosphere.

Rogers, R. Clayton↗
NASA NTRS1986

Effects of test facility contaminants on supersonic hydrogen-air diffusion flames

Results are presented from an analytical assessment of the effects of NO and H2O in air on the ignition and reaction of hydrogen. Three flow models of the burning process were used, each including a 32 reaction chemistry mechanism. These models were a plug flow reactor to determine ignition and reaction times; a well-stirred reactor to assess flame stability or blow-off, and a parabolic Navier Stokes code to examine the diffusion flame combustion. The diffusion flame was computed for a cold supersonic H2 jet coaxial with a supersonic air stream at a static temperature of 1100 K and a pressure of 1 atmosphere.

Rogers, R. Clayton↗
NASA NTRS1995

Heterogeneous reactions of HNO3(g) + NaCl(s) yields HCl(g) + NaNO3(s) and N2O5(g) + NaCl(s) yields ClNO2(g) + NaNO3(s)

The heterogeneous reactions of HNO3(g) + NaCl(s) yields HCl(g) + NaNO3(s) (eq 1) and N2O5(g) + NaCl(s) yields ClNO2(g) + NaNO3(S) (eq 2) were investigated over the temperature range 223-296 K in a flow-tube reactor coupled to a quadrupole mass spectrometer. Either a chemical ionization mass spectrometer (CIMS) or an electron-impact ionization mass spectrometer (EIMS) was used to provide suitable detection sensitivity and selectivity. In order to mimic atmospheric conditions, partial pressures of HNO3 and N2O5 in the range 6 x 10(exp -8) - 2 x 10(exp -6) Torr were used. Granule sizes and surface roughness of the solid NaCl substrates were determined by using a scanning electron microscope. For dry NaCl substrates, decay rates of HNO3 were used to obtain gamma(1) = 0.013 +/- 0.004 (1sigma) at 296 K and > 0.008 at 223 K, respectively. The error quoted is the statistical error. After all corrections were made, the overall error, including systematic error, was estimated to be about a factor of 2. HCl was found to be the sole gas-phase product of reaction 1. The mechanism changed from heterogeneous reaction to predominantly physical adsorption when the reactor was cooled from 296 to 223 K. For reaction 2 using dry salts, gamma(2) was found to be less than 1.0 x 10(exp -4) at both 223 and 296 K. The gas-phase reaction product was identified as ClNO2 in previous studies using an infrared spectrometer. An enhancement in reaction probability was observed if water was not completely removed from salt surfaces, probably due to the reaction of N2O5(g) + H2O(s) yields 2HNO3(g). Our results are compared with previous literature values obtained using different experimental techniques and conditions. The implications of the present results for the enhancement of the hydrogen chloride column density in the lower stratosphere after the El Chichon volcanic eruption and for the chemistry of HCl and HNO3 in the marine troposphere are discussed.

Leu, Ming-Taun↗
NASA NTRS2000

NASA Lessons Learned from Space Lubricated Mechanisms

This document reviews the lessons learned from short-life and long life lubricated space mechanisms. A short-life lubricated mechanisms complete their life test qualification requirements after a few cycles. The mechanisms include the hinges, motors and bearings for deployment, release mechanisms, latches, release springs and support shops. Performance testing can be difficult and expensive but must be accomplished. A long-life lubricated mechanisms requires up to 5 years of life testing, or 10 to 100 years of successful flight. The long-life mechanisms include reaction wheels, momentum wheels, antenna gimbals, solar array drives, gyros and despin mechanisms. Several instances of how a mechanisms failed either in test, or in space use, and the lessons learned from these failures are reviewed. The effect of the movement away from CFC-113 cleaning solvent to ODC (Ozone-Depleting Chemical) -free is reviewed, and some of the alternatives are discussed.

Predmore, Roamer E.↗
NASA NTRS1987

Potential energy surfaces for atomic oxygen reactions: Formation of singlet and triplet biradicals as primary reaction products with unsaturated organic molecules

The experimental study of the interaction of atomic oxygen with organic polymer films under LEO conditions has been hampered by the inability to conduct detailed experiments in situ. As a result, studies of the mechanism of oxygen atom reactions have relied on laboratory O-atom sources that do not fully reproduce the orbital environment. For example, it is well established that only ground electronic state O atoms are present at LEO, yet most ground-based sources are known to produce singlet O atoms and molecules and ions in addition to O(3P). Engineers should not rely on such facilities unless it can be demonstrated either that these different O species are inert or that they react in the same fashion as ground state atoms. Ab initio quantum chemical calculations have been aimed at elucidating the biradical intermediates formed during the electrophilic addition of ground and excited-state O atoms to carbon-carbon double bonds in small olefins and aromatic molecules. These biradicals are critical intermediates in any possible insertion, addition and elimination reaction mechanisms. Through these calculations, we will be able to comment on the relative importance of these pathways for O(3P) and O(1D) reactions. The reactions of O atoms with ethylene and benzene are used to illustrate the important features of the mechanisms of atomic oxygen reaction with unsaturated organic compounds and polymeric materials.

Jaffe, Richard L.↗
NASA NTRS1973

Rates and mechanisms of the atomic oxygen reaction with nickel at elevated temperatures

The oxidation of nickel by atomic oxygen at pressure from 1 to 45 N/sq m between 1050 and 1250 K was investigated. In these ranges, the oxidation was found to follow the parobolic rate law, viz., K sub p = 0.0000114 exp(-13410/T) g squared/cm4/sec for films of greater than 1 micron thickness and was pressure independent. The activation enthalpy for the oxidation reaction was 112 + or - 11 kj/mole (27 + or - 3 kcal/mole). Of a number of possible mechanisms and defect structures considered, it was shown that the most likely was a saturated surface defect model for atomic oxidation, based on reaction activation enthalpies, impurity effects, pressure independence, and magnitudes of rates. A model judged somewhat less likely was one having doubly ionized cationic defects rate controlling in both atomic and molecular oxygen. From comparisons of the appropriate processes, the following enthalpy values were derived: enthalpy of activation (Ni diffusion in Ni0) = 110 + or - 30 kj/mole and standard enthalpy change for reaction formation (doubly ionized cation vacancies in Ni0 from atomic oxygen)= -9 + or - 25 kj/mole.

Christian, J. D.↗