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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 829 records · Page 46
All sourcesNASA NTRSDOE OSTI
NASA NTRS1994

New calculations on the ion-molecule processes C2H2(+) + H2 --> C2H3(+) + H and C2H2(+) + H2 --> C2H4+

New high-level quantum chemical calculations have been undertaken to understand the rates and mechanisms of the reactive and associative channels for the reactants C2H2(+) + H2. The reactive channel, which produces C2H3(+) + H, has been shown to be slightly endothermic, confirming earlier calculations at a somewhat lower level and in agreement with some recent experimental work. The associative channel, leading to C2H4+, has been shown to proceed via a transition state with negative energy relative to the reactants, so that association is predicted to be efficient. This result is in conflict with an earlier theoretical study but in agreement with low-temperature experimental measurements.

NASA Discipline Exobiology↗
NASA NTRS1996

Kinetic and mechanistic analysis of nonenzymatic, template-directed oligoribonucleotide ligation

The role of divalent cations in the mechanism of pyrophosphate-activated, template-directed oligoribonucleotide ligation has been investigated. The dependence of the reaction rate on Mg2+ concentration suggests a kinetic scheme in which a Mg2+ ion must bind before ligation can proceed. Mn2+, Ca2+, Sr2+, and Ba2+ can also catalyze the reaction. Although Pb2+ and Zn2+ do not catalyze the reaction in the absence of other divalent ions, they significantly modulate the reaction rate when added in the presence of Mg2+, with Pb2+ stimulating the reaction (up to 65-fold) and Zn2+ inhibiting the reaction. The logarithm of the ligation rate increases linearly, with slope of 0.95, as a function of pH, indicating that the reaction involves a single critical deprotonation step. The ligation rates observed with the different divalent metal ion catalysts (Mn2+ > Mg2+ > Ca2+ > Sr2+ = Ba2+) vary inversely with the pKa values of their bound water molecules. The pH profile and these relative ligation rates suggest a mechanism in which a metal-bound hydroxide ion located near the ligation junction promotes catalysis, most likely by deprotonation of the hydroxl nucleophile. The effects of changing either the leaving group or the attacking hydroxyl, together with the large delta S(++) value for oligonucleotide ligation (about -20 eu), are consistent with an associative transition state.

Non-NASA Center↗
NASA NTRS1991

Catalysis of hydrolysis and nucleophilic substitution at the P-N bond of phosphoimidazolide-activated nucleotides in phosphate buffers

Phosphoimidazolide-activated derivatives of guanosine and cytidine 5'-monophosphates, henceforth called ImpN's, exhibit enhanced rates of degradation in the presence of aqueous inorganic phosphate in the range 4.0 < or = pH < or = 8.6. This degradation is been attributed to (i) nucleophilic substitution of the imidazolide and (ii) catalysis of the P-N bond hydrolysis by phosphate. The first reaction results in the formation of nucleoside 5'-diphosphate and the second in nucleoside 5'-monophosphate. Analysis of the observed rates as well as the product ratios as a function of pH and phosphate concentration allow distinction between various mechanistic possibilities. The results show that both H2PO4- and HPO4(2-) participate in both hydrolysis and nucleophilic substitution. Statistically corrected biomolecular rate constants indicate that the dianion is 4 times more effective as a general base than the monoanion, and 8 times more effective as nucleophile. The low Bronsted value beta = 0.15 calculated for these phosphate species, presumed to act as general bases in facilitating water attack, is consistent with the fact that catalysis of the hydrolysis of the P-N bond in ImpN's has not been detected before. The beta nuc = 0.35 calculated for water, H2PO4-, HPO4(2-), and hydroxide acting as nucleophiles indicates a more associative transition state for nucleotidyl (O2POR- with R = nucleoside) transfers than that observed for phosphoryl (PO3(2-)) transfers (beta nuc = 0.25). With respect to the stability/reactivity of ImpN's under prebiotic conditions, our study shows that these materials would not suffer additional degradation due to inorganic phosphate, assuming the concentrations of phosphate, Pi, on prebiotic Earth were similar to those in the present oceans ([Pi] approximately 2.25 micromoles).

NASA Discipline Number 52-20↗
NASA NTRS1992

Design of potent substrate-analogue inhibitors of canine renin

Through a systematic study of structure-activity relationships, we designed potent renin inhibitors for use in dog models. In assays against dog plasma renin at neutral pH, we found that, as in previous studies of rat renin inhibitors, the structure at the P2 position appears to be important for potency. The substitution of Val for His at this position increases potency by one order of magnitude. At the P3 position, potency appears to depend on a hydrophobic side chain that does not necessarily have to be aromatic. Our results also support the approach of optimizing potency in a renin inhibitor by introducing a moiety that promotes aqueous solubility (an amino group) at the C-terminus of the substrate analogue. In the design of potent dog plasma renin inhibitors, the influence of the transition-state residue 4(S)-amino-3(S)-hydroxy-5-cyclohexylpentanoic acid (ACHPA)-commonly used as a substitute for the scissile-bond dipeptide to boost potency-is not obvious, and appears to be sequence dependent. The canine renin inhibitor Ac-paF-Pro-Phe-Val-statine-Leu-Phe-paF-NH2 (compound 15; IC50 of 1.7 nM against dog plasma renin at pH 7.4; statine, 4(S)-amino-3(S)-hydroxy-6-methylheptanoic acid; paF, para-aminophenylalanine) had a potent hypotensive effect when infused intravenously into conscious, sodium-depleted, normotensive dogs. Also, compound 15 concurrently inhibited plasma renin activity and had a profound diuretic effect.

Non-NASA Center↗
NASA NTRS2003

Helicity in supercritical temporal mixing layers

Databases of transitional states obtained from Direct Numerical Simulations (DNS) of temporal, supercritical mixing layers for two species systems, 02/H2 and C7Hle/N2, are analyzed to elucidate species-specific turbulence aspects.

helicity supercritical flows↗
NASA NTRS1994

An Empirical Expression for Line Widths of Ammonia from Far-Infrared Measurements

The hydrogen- and self-broadened line widths of 116 (sup 14)NH(sub 3) ground state transitions with J,K = 1,0 to 10,10 have been measured at 0.0006 cm(sup -1) resolution using a Bruker spectrometer between 40 to 210 cm(sup -1). These experimental widths have been reproduced to 2.4% and 11% respectively using an heuristically derived expression of the form....

remote sensing planets↗
NASA NTRS2004

Experimentally Determined Plasma Parameters in a 30 cm Ion Engine

Single planar Langmuir probes and fiber optic probes are used to concurrently measure the plasma properties and neutral density variation in a 30cm diameter ion engine discharge chamber, from the immediate vicinity of the keeper to the near grid plasma region. The fiber optic probe consists of a collimated optical fiber recessed into a double bore ceramic tube fitted with a stainless steel light-limiting window. The optical fiber probe is used to measure the emission intensity of excited neutral xenon for a small volume of plasma, at various radial and axial locations. The single Langmuir probes, are used to generate current-voltage characteristics at a total of 140 spatial locations inside the discharge chamber. Assuming a maxwellian distribution for the electron population, the Langmuir probe traces provide spatially resolved measurements of plasma potential, electron temperature, and plasma density. Data reduction for the NSTAR TH8 and TH15 throttle points indicates an electron temperature range of 1 to 7.9 eV and an electron density range of 4e10 to le13 cm(sup -3), throughout the discharge chamber, consistent with the results in the literature. Plasma potential estimates, computed from the first derivative of the probe characteristic, indicate potential from 0.5V to 11V above the discharge voltage along the thruster centerline. These values are believed to be excessively high due to the sampling of the primary electron population along the thruster centerline. Relative neutral density profiles are also obtained with a fiber optic probe sampling photon flux from the 823.1 nm excited to ground state transition. Plasma parameter measurements and neutral density profiles will be presented as a function of probe location and engine discharge conditions. A discussion of the measured electron energy distribution function will also be presented, with regards to variation from pure maxwellian. It has been found that there is a distinct primary population found along the thruster centerline, which causes estimates of electron temperature, electron density, and plasma potential, to err on the high side, due this energetic population. Computation of the energy distribution fimction of the plasma clearly indicates the presence of primaries, whose presence become less obvious with radial distance from the main discharge plume.

near grid plasma↗
NASA NTRS2005

A Priori Analysis of Subgrid-Scale Models for Large Eddy Simulations of Supercritical Binary-Species Mixing Layers

Models for large eddy simulation (LES) are assessed on a database obtained from direct numerical simulations (DNS) of supercritical binary-species temporal mixing layers. The analysis is performed at the DNS transitional states for heptane/nitrogen, oxygen/hydrogen and oxygen/helium mixing layers. The incorporation of simplifying assumptions that are validated on the DNS database leads to a set of LES equations that requires only models for the subgrid scale (SGS) fluxes, which arise from filtering the convective terms in the DNS equations. Constant-coefficient versions of three different models for the SGS fluxes are assessed and calibrated. The Smagorinsky SGS-flux model shows poor correlations with the SGS fluxes, while the Gradient and Similarity models have high correlations, as well as good quantitative agreement with the SGS fluxes when the calibrated coefficients are used.

turbulence↗
NASA NTRS2006

Modeling Chemical Growth Processes in Titan's Atmosphere: 1. Theoretical Rates for Reactions between Benzene and the Ethynyl (C2H) and Cyano (CN) Radicals at Low Temperature and Pressure

Density functional theory calculations at the B3LYP/6-31+G** level were employed to characterize the critical points for adducts, isomers, products, and intervening transition states for the reactions between benzene and the ethynyl (C2H) or cyano (CN) radicals. Both addition reactions were found to have no barriers in their entrance channels, making them efficient at the low temperature and pressure conditions that prevail in the haze-forming region of Titan's atmosphere as well as in the dense interstellar medium (ISM). The dominant products are ethynylbenzene (C6H5C2H) and cyanobenzene (C6H5CN). Hydrogen abstraction reactions were also characterized but found to be non-competitive. Trajectory calculations based on potentials fit to about 600 points calculated at the ROMP2/6-31+G** level for each interaction surface were used to determine reaction rates. The rates incorporated any necessary corrections for back reactions as ascertained from a multiwell treatment used to determine outcome distributions over the range of temperatures and pressures pertinent to Titan and the ISM and are in good agreement with the limited available experimental data.

Woon, David E.↗
NASA NTRS2008

Perturbation Effects on a Supercritical C7H16/N2 Mixing Layer

A computational-simulation study has been presented of effects of perturbation wavelengths and initial Reynolds numbers on the transition to turbulence of a heptane/nitrogen mixing layer at supercritical pressure. The governing equations for the simulations were the same as those of related prior studies reported in NASA Tech Briefs. Two-dimensional (2D) simulations were performed with initially im posed span wise perturbations whereas three-dimensional (3D) simulations had both streamwise and spanwise initial perturbations. The 2D simulations were undertaken to ascertain whether perturbations having the shortest unstable wavelength obtained from a linear stability analysis for inviscid flow are unstable in viscous nonlinear flows. The goal of the 3D simulations was to ascertain whether perturbing the mixing layer at different wavelengths affects the transition to turbulence. It was found that transitions to turbulence can be obtained at different perturbation wavelengths, provided that they are longer than the shortest unstable wavelength as determined by 2D linear stability analysis for the inviscid case and that the initial Reynolds number is proportionally increased as the wavelength is decreased. The transitional states thus obtained display different dynamic and mixture characteristics, departing strongly from the behaviors of perfect gases and ideal mixtures.

Okongo'o, Nora↗
NASA NTRS2008

Synchrotron Photoionization Mass Spectrometry Measurements of Kinetics and Product Formation in the Allyl Radical (H2CCHCH2)Self Reaction

Product channels for the self-reaction of the resonance-stabilized allyl radical, C3H5 + C3H5, have been studied with isomeric specificity at temperatures from 300-600 K and pressures from 1-6 Torr using time-resolved multiplexed photoionization mass spectrometry. Under these conditions 1,5-hexadiene was the only C6H10 product isomer detected. The lack of isomerization of the C6H10 product is in marked contrast to the C6H6 product in the related C3H3 + C3H3 reaction, and is due to the more saturated electronic structure of the C6H10 system. The disproportionation product channel, yielding allene + propene, was also detected, with an upper limit on the branching fraction relative to recombination of 0.03. Analysis of the allyl radical decay at 298 K yielded a total rate coefficient of (2.7 +/- 0.8) x 10(exp -11) cu cm/molecule/s, in good agreement with pre.vious experimental measurements using ultraviolet kinetic absorption spectroscopy and a recent theoretical determination using variable reaction coordinate transition state theory. This result provides independent indirect support for the literature value of the allyl radical ultraviolet absorption cross-section near 223 nm.

Selby, Talitha M.↗
NASA NTRS2009

Targeting Ballistic Lunar Capture Trajectories Using Periodic Orbits in the Sun-Earth CRTBP

A particular periodic orbit in the Earth-Sun circular restricted three body problem is shown to have the characteristics needed for a ballistic lunar capture transfer. An injection from a circular parking orbit into the periodic orbit serves as an initial guess for a targeting algorithm. By targeting appropriate parameters incrementally in increasingly complicated force models and using precise derivatives calculated from the state transition matrix, a reliable algorithm is produced. Ballistic lunar capture trajectories in restricted four body systems are shown to be able to be produced in a systematic way.

Cooley, D.S.↗
NASA NTRS2010

Model-Driven Development of Reliable Avionics Architectures for Lunar Surface Systems

This paper discusses a method used for the systematic improvement of NASA s Lunar Surface Systems avionics architectures in the area of reliability and fault-tolerance. This approach utilizes an integrated system model to determine the effects of component failure on the system s ability to provide critical functions. A Markov model of the potential degraded system modes is created to characterize the probability of these degraded modes, and the system model is run for each Markov state to determine its status (operational or system loss). The probabilistic results from the Markov model are first produced from state transition rates based on NASA data for heritage failure rate data of similar components. An additional set of probabilistic results are created from a representative set of failure rates developed for this study, for a variety of component quality grades (space-rated, mil-spec, ruggedized, and commercial). The results show that careful application of redundancy and selected component improvement should result in Lunar Surface Systems architectures that exhibit an appropriate degree of fault-tolerance, reliability, performance, and affordability.

Borer, Nicholas↗
NASA NTRS2011

Small-Scale Dissipation in Binary-Species Transitional Mixing Layers

Motivated by large eddy simulation (LES) modeling of supercritical turbulent flows, transitional states of databases obtained from direct numerical simulations (DNS) of binary-species supercritical temporal mixing layers were examined to understand the subgrid-scale dissipation, and its variation with filter size. Examination of the DSN-scale domain- averaged dissipation confirms previous findings that, out of the three modes of viscous, temperature and species-mass dissipation, the species-mass dissipation is the main contributor to the total dissipation. The results revealed that the percentage of species-mass by total dissipation is nearly invariant across species systems and initial conditions. This dominance of the species-mass dissipation is due to high-density-gradient magnitude (HDGM) regions populating the flow under the supercritical conditions of the simulations; such regions have also been observed in fully turbulent supercritical flows. The domain average being the result of both the local values and the extent of the HDGM regions, the expectations were that the response to filtering would vary with these flow characteristics. All filtering here is performed in the dissipation range of the Kolmogorov spectrum, at filter sizes from 4 to 16 times the DNS grid spacing. The small-scale (subgrid scale, SGS) dissipation was found by subtracting the filtered-field dissipation from the DNS-field dissipation. In contrast to the DNS dissipation, the SGS dissipation is not necessarily positive; negative values indicate backscatter. Backscatter was shown to be spatially widespread in all modes of dissipation and in the total dissipation (25 to 60 percent of the domain). The maximum magnitude of the negative subgrid- scale dissipation was as much as 17 percent of the maximum positive subgrid- scale dissipation, indicating that, not only is backscatter spatially widespread in these flows, but it is considerable in magnitude and cannot be ignored for the purposes of LES modeling. The Smagorinsky model, for example, is unsuited for modeling SGS fluxes in the LES because it cannot render backscatter. With increased filter size, there is only a modest decrease in the spatial extent of backscatter. The implication is that even at large LES grid spacing, the issue of backscatter and related SGS-flux modeling decisions are unavoidable. As a fraction of the total dissipation, the small-scale dissipation is between 10 and 30 percent of the total dissipation for a filter size that is four times the DNS grid spacing, with all OH cases bunched at 10 percent, and the HN cases spanning 24 30 percent. A scale similarity was found in that the domain-average proportion of each small-scale dissipation mode, with respect to the total small-scale dissipation, is very similar to equivalent results at the DNS scale. With increasing filter size, the proportion of the small-scale dissipation in the dissipation increases substantially, although not quite proportionally. When the filter size increases by four-fold, 52 percent for all OH runs, and 70 percent for HN runs, of the dissipation is contained in the subgrid-scale portion with virtually no dependence on the initial conditions of the DNS. The indications from the dissipation analysis are that modeling efforts in LES of thermodynamically supercritical flows should be focused primarily on mass-flux effects, with temperature and viscous effects being secondary. The analysis also reveals a physical justification for scale-similarity type models, although the suitability of these will need to be confirmed in a posteriori studies.

Bellan, Josette↗
NASA NTRS2011

Environmental Signatures for Habitability: What to Measure and How to Rank the Habitability Potential of Mars

The environmental signatures for habitability are not necessarily biosignatures, even though on Earth, they are definitive proof of habitability. It is the constant overprint of the chemical signatures of life that makes it difficult to recognize the chemical and physical properties of a potentially habitable environment as distinct from an inhabited one. Mars Science Laboratory (MSL) will soon embark on a mission to Mars to assess its past or present habitability, so it is useful to examine how we measure habitability on Earth and prepare for how that approach may differ for Mars. This exercise includes: (a) articulation of fundamental assumptions about habitability, (b) an inventory of factors that affect habitability, (c) development of metrics, measurement approach and implementation, and (d) a new classification scheme for planetary habitability that goes beyond the binary "yes" or "no." There may be dozens of factors that affect habitability and they can be weighted as a function of specific environment. However a robotic, in situ investigation even on Earth has constraints that prevent the measurement of every environmental factor, so metrics must be reduced to the most relevant subset, given available time, cost, technical feasibility and scientific importance. Many of the factors could be measured with a combination of orbital data and the MSL payload. We propose that, at a minimum, a designation of high habitability potential requires the following conditions be met: (a) thermally stable with respect to extremes and frequency of fluctuation, (b) has more than one energy source, (c) sufficient chemical diversity to make compounds with covalent and hydrogen bonding, (d) can moderate ionizing radiation enough to allow a stable or evolving pool of organic molecules, (e) must have water or other high quality polar solvent, (f) must be able to renew chemical resources (e.g., plate tectonics, volcanism or something else we haven't envisioned). A measurement approach we have taken to measure habitability on Earth is : 1. Study remote sensing data, maps, etc. 2. Decide how big an area to measure. 3. Determine the spatial sampling rate. 4. Determine the temporal sampling rate. 5. Determine the order of measurements 6. Decide where to begin measurements 7. Select locations at field site and proceed While science drives each of the steps, there are additional constraints, e.g., technical, time, cost, safety (risk). This approach is also executable on Mars. Measurement of past habitability is more challenging both for Earth and Mars where access to the past means subsurface access and confrontation with unknowns about preservation of the martian past. Some environments preserve evidence of past habitability better than others, and this is where selection of the landing site to maximize the preservation potential of habitability indicators will be key. Mars presents an opportunity to discover transitional states between habitable or not, and we offer a ranking scale for planetary habitability with Mars as the second test subject: CLASS ONE Uninhabitable and likely has never been so CLASS TWO Has a high potential but no confirmed observation of life (as defined above) CLASS THREE Inhabited (we find life) 3-A Globally inhabited 3-B Primitive life; early in its evolution, but not yet globally established 3-C Exists only in refugia -- planet heading toward class four CLASS FOUR Post-habitable (there once was life, but now it's gone) MSL provides an opportunity to carefully investigate the habitability of at least one site on Mars and it will reveal much about the possible states of planetary habitability

Conrad, Pamela G.↗
NASA NTRS2011

Effects of Cavities and Protuberances on Transition over Hypersonic Vehicles

Surface protuberances and cavities on a hypersonic vehicle are known to cause several aerodynamic or aerothermodynamic issues. Most important of all, premature transition due to these surface irregularities can lead to a significant rise in surface heating. To help understand laminar-turbulent transition induced by protuberances or cavities on a Crew Exploration Vehicle (CEV) surface, high-fidelity numerical simulations are carried out for both types of trips on a CEV wind tunnel model. Due to the large bluntness, these surface irregularities reside in an accelerating subsonic boundary layer. For the Mach 6 wind tunnel conditions with a roughness Reynolds number Re(sub kk) of 800, it was found that a protuberance with a height to boundary layer thickness ratio of 0.73 leads to strong wake instability and spontaneous vortex shedding, while a cavity with identical geometry only causes a rather weak flow unsteadiness. The same cavity with a larger Reynolds number also leads to similar spontaneous vortex shedding and wake instability. The wake development and the formation of hairpin vortices for both protuberance and cavity were found to be qualitatively similar to that observed for an isolated hemisphere submerged in a subsonic, low speed flat-plate boundary layer. However, the shed vortices and their accompanying instability waves were found to be slightly stabilized downstream by the accelerating boundary layer along the CEV surface. Despite this stabilizing influence, it was found that the wake instability spreads substantially in both wall-normal and azimuthal directions as the flow is evolving towards a transitional state. Similarities and differences between the wake instability behind a protuberance and a cavity are investigated. Computations for the Mach 6 boundary layer over a slender cylindrical roughness element with a height to the boundary layer thickness of about 1.1 also shows spontaneous vortex shedding and strong wake instability. Comparisons of detailed flow structures associated with protuberances at subsonic and supersonic edge Mach numbers indicate distinctively different instability mechanisms.

Chang, Chau-Lyan↗