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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
NASA NTRS2018

Chain Formation as a Mechanism for Mass-Independent Fractionation of Sulfur Isotopes in the Archean Atmosphere

The anomalous abundances of sulfur isotopes in ancient sediments provide the strongest evidence for an anoxic atmosphere prior to ∼2.45 Ga, but the mechanism for producing this ‘mass-independent’ fractionation pattern remains in question. The prevailing hypothesis has been that it is created by differences in the UV photolysis rates of different SO2 isotopologues. We investigate here a recently proposed additional source of fractionation during gas-phase formation of elemental sulfur (S4 and S8). Because two minor S isotopes rarely occur in the same chain, the longer S4 and S8 chains should be strongly, and roughly equally, depleted in all minor isotopes. This gives rise to negative Δ(exp 33)S values and positive Δ(exp 33)S values in elemental sulfur—just the opposite of (and much larger than) what is predicted from SO2 photolysis itself. Back-reactions during chain formation, specifically photolysis of S2 and S3, pass sulfur having the opposite fractionation back to atomic S, and thence to other sulfur species, causing H2S, SO2, sulfate, and short-chain elemental sulfur to have positive Δ(exp 33)S and negative Δ(exp 33)S. Positive Δ(exp 33)S values in elemental sulfur produced in laboratory SO2 photolysis experiments could be caused by the initial fractionation during photolysis, combined with rapid condensation of short-chain sulfur species on the walls of the reaction chamber, along with a scarcity of back-reactions. The simulated fractionations produced by the chain formation mechanism do not directly match fractionations from the rock record. The mismatch might be explained if the isotopic signals leaving the atmosphere were significantly modulated by life, by uncertainties in the rates of reactions of both major and minor isotopic sulfur species, or by the relatively large potential range of atmospheric parameters. Further work is needed to better constrain these uncertainties, but this novel mechanism suggests new avenues to explore in our search for a explanation for the S-MIF record.

C. E. Harman↗
NASA NTRS1996

A search for HCCN in molecular clouds

We have conducted a deep search for HCCN towards the dark cloud TMC-l and several GMC's via its N(J) = 1(2)-->0(1) transition. HCCN was not detected in any of these sources. Towards TMC-l, assuming optically thin emission, the total column density upper limit is NHCCN < or = 2 x 10(12) cm-2, which corresponds to a fractional abundance upper limit with respect to molecular hydrogen of fHCCN < or = 2 x 10(-10). We find the abundance ratio of HCN:HCCN:HCCCN in TMC-l to be l : <0.01 : 0.3, which suggests that carbon-chain growth by the addition of single carbon atoms may not be efficient under dark cloud conditions. The HCCN abundance limit also places constraints on the branching ratio for the products of the dissociative electron recombination H3C2N+ + e.

Non-NASA Center↗
NASA NTRS1995

Fibonacci chain polynomials: Identities from self-similarity

Fibonacci chains are special diatomic, harmonic chains with uniform nearest neighbor interaction and two kinds of atoms (mass-ratio r) arranged according to the self-similar binary Fibonacci sequence ABAABABA..., which is obtained by repeated substitution of A yields AB and B yields A. The implications of the self-similarity of this sequence for the associated orthogonal polynomial systems which govern these Fibonacci chains with fixed mass-ratio r are studied.

Lang, Wolfdieter↗
NASA NTRS2011

Discovery of Interstellar Anions in Cepheus and Auriga

We report the detection of microwave emission lines from the hydrocarbon anion C6H(-) and its parent neutral C6H in the star-forming region LI251 A (in Cepheus), and the pre-stellar core LI512 (in Auriga). The carbon chain-bearing species C4H, HC3N, HC5N, HC7N, and C3S are also detected in large abundances. The observations of L1251A constitute the first detections of anions and long-chain polyynes and cyanopolyynes (with more than five carbon atoms) in the Cepheus Flare star-forming region, and the first detection of anions in the vicinity of a protostar outside of the Taurus molecular cloud complex, indicating a possible wider importance for anions in the chemistry of star formation. Rotational excitation temperatures have been derived from the HC3N hyperfine structure lines and are found to be 6.2 K for L1251A and 8.7 K for LI5l2. The anion-to-neutral ratios are 3.6% and 4.1%, respectively, which are within the range of values previously observed in the interstellar medium, and suggest a relative uniformity in the processes governing anion abundances in different dense interstellar clouds. This research contributes toward the growing body of evidence that carbon chain anions are relatively abundant in interstellar clouds throughout the Galaxy, but especially in the regions of relatively high density and high depletion surrounding pre-stellar cores and young, embedded protostars.

Cordiner, M. A.↗
NASA NTRS2012

Gas-Grain Models for Interstellar Anion Chemistry

Long-chain hydrocarbon anions C(sub n) H(-) (n = 4, 6, 8) have recently been found to be abundant in a variety of interstellar clouds. In order to explain their large abundances in the denser (prestellar/protostellar) environments, new chemical models are constructed that include gas-grain interactions. Models including accretion of gas-phase species onto dust grains and cosmic-ray-induced desorption of atoms are able to reproduce the observed anion-to-neutral ratios, as well as the absolute abundances of anionic and neutral carbon chains, with a reasonable degree of accuracy. Due to their destructive effects, the depletion of oxygen atoms onto dust results in substantially greater polyyne and anion abundances in high-density gas (with n(sub H2) approx > / cubic cm). The large abundances of carbon-chain-bearing species observed in the envelopes of protostars such as L1527 can thus be explained without the need for warm carbon-chain chemistry. The C6H(-) anion-to-neutral ratio is found to be most sensitive to the atomic O and H abundances and the electron density. Therefore, as a core evolves, falling atomic abundances and rising electron densities are found to result in increasing anion-to-neutral ratios. Inclusion of cosmic-ray desorption of atoms in high-density models delays freeze-out, which results in a more temporally stable anion-to-neutral ratio, in better agreement with observations. Our models include reactions between oxygen atoms and carbon-chain anions to produce carbon-chain-oxide species C6O, C7O, HC6O, and HC7O, the abundances of which depend on the assumed branching ratios for associative electron detachment

Cordiner, M. A.↗
NASA NTRS1955

Chemical Action of Halogenated Agents in Fire Extinguishing

The action of halogenated agents in preventing flame propagation in fuel-air mixtures in laboratory tests is discussed in terms of a possible chemical mechanism. The mechanism chosen is that of chain-breaking reactions between agent and active particles (hydrogen and oxygen atoms and hydroxyl radicsls). Data from the literature on the flammability peaks of n-heptane agent-air mixtures are treated. Ratings of agent effectiveness in terms of the fuel equivalent of the agent, based on both fuel and agent concentrations at the peak, are proposed as preferable to ratings in terms of agent concentration alone. These fuel-equivalent ratings are roughly correlated by reactivities assigned to halogen and hydrogen atoms in the agent molecules. It is concluded that the presence of hydrogen in agent need not reduce its fire-fighting ability, provided there is enough halogen to make the agent nonflammable. A method is presented for estimating from quenching-distance data a rate constant for the reaction of agent with active particles. A quantitative result is obtained for methyl bromide. This rate constant predicts the observed peak concentration of methyl bromide quite well. However, more data are needed to prove the validity of the method. The assumption that hal.ogenatedagents act mainly by chain-bresking reactions with active particles is consistent with the experimental facts and should help guide the selection of agents for further tests.

Belles, Frank E.↗
NASA NTRS1998

In Situ Infrared Spectroscopy of the Gaseous Species Present in a Diamond Chemical Vapor Deposition System

We interfaced a Hot-Filament Chemical Vapor Deposition (HFCVD) system to the emission port of an FT-IR spectrometer, in order to study the gas phase species present during the deposition of diamond thin films. The implementation of the infrared (IR) emission technique in situ allowed the study of various carbon-containing species believed to be crucial in diamond film growth. The two IR-active vibrational fundamentals of methane, v(3)(f2) and v(4)(f2), were observed at three different filament temperatures: 1000, 1500 and 2000 C. However, the net signal of v(3) was emission, while that of v(4) was absorption. These results indicate that the v(4) fundamental is excited beyond equilibrium, while the v(3) fundamental remains mostly in the ground state. This is due to the small concentration of methane, the low energy of v(4) compared to v(3) or to the Hz vibrational mode, and symmetry considerations that forbid interaction among the four fundamentals of methane. Thus, the excitation of v(3) is more likely than its decay under HFCVD conditions, producing a non-equilibrium population. At a filament temperature of 2000 C, the v(3) (sigma(+)(3)) fundamental of acetylene and a band at 1328 cm-l also ascribed to acetylene (v5 (pi(U)) + v4) appear in net absorption. This correlates well with the onset of molecular hydrogen breaking by the filament, which occurs at temperatures around 2000 C and above. The hydrogen atoms produced in this heterogeneous reaction give rise to a chain of reactions that lead to acetylene, among other carbonaceous species.

Morell, G.↗
NASA NTRS2003

Package for Interactive Analysis of Line Emission (Analysis of UV-X-Ray High-Resolution Emission Spectra)

PINTofALE is an IDL based package to analyze high-resolution grating spectra. The first version was made available to the public on 3 February 2001. Since then we have carried out numerous changes, and the current release is version 1.5, released on 9 October 2002. The changes include upgrades to handle higher versions of IDL, the new version of the CHIANTI database (v4), major enhancements in user-friendliness, improved handling of response matrices, the ability to handle 24-bit color, access to the Atomic Plasma Emission Database (APED), and beta releases of Markov Chain Monte Carlo (MCMC) based DEM fitting routines. Plans for the future include: inclusion of MCMC techniques in the fitting programs, enhanced graphics capabilities, an overhaul of the line and continuum database structure, and bug fixes. In September 2002, we hired a data analyst (LiWei Lin) to work on PINTofALE. Mr.Lin is concentrating on incorporating MCMC as well as simpler Monte-Carlo techniques, fast RMF convolution, etc., into the code base, as well as reviewing the existing documentation and searching for bugs. A detailed description of the package, together with fairly detailed documentation, example walks-throughs, and downloadable tar files, are available on-line from http://hea-www. harvard.edu/PINTofALE/

Kashyap, Vinay↗
NASA NTRS1971

EPR-atomic scale experimental stress analysis

Electron paramagnetic resonance atomic scale stress analysis of high polymer fibers and rubber, measuring chain scission and bond rupture for different loading histories

Devries, K. L.↗
NASA NTRS1980

Use of generalized population ratios to obtain Fe XV line intensities and linewidths at high electron densities

A generalized method for obtaining individual level population ratios is used to obtain relative intensities of extreme ultraviolet Fe XV emission lines in the range 284-500 A, which are density dependent for electron densities in the tokamak regime or higher. Four lines in particular are found to attain quite high intensities in the high-density limit. The same calculation provides inelastic contributions to linewidths. The method connects level populations and level widths through total probabilities t(ij), related to 'taboo' probabilities of Markov chain theory. The t(ij) are here evaluated for a real atomic system, being therefore of potential interest to random-walk theorists who have been limited to idealized systems characterized by simplified transition schemes.

Kastner, S. O.↗
NASA NTRS1989

Low dielectric thermoplastic polyimide resin

NASA-Langley studies of polymer structure-property relationships have led to the development of a method for the reduction of dielectric constants in polyimides through chemical alterations of polymer backbone composition to reduce chain-chain electronic interactions, as well as through the incorporation of fluorine atoms into the polymer molecular structure. Still-greater dielectric constant reductions are obtainable by means of a physical incorporation of diamic acid additives into these low-dielectric polyimide systems; the resulting thermoplastic resins are applicable to polymer matrices for composite structural materials.

Stoakley, D. M.↗
NASA NTRS1991

Theoretical studies of the extraterrestrial chemistry of biogenic elements and compounds

Organic compounds, molecules related to those in living systems, are found in many different extraterrestrial environments. The study of organic astrochemistry is important to exobiology both because it demonstrates the ubiquity of processes which led to life on Earth and because the dust clouds where molecules are found are analogs of the solar nebula from which the Earth formed. In the long chain of events leading from the Big Bang, and a universe composed of atomic hydrogen and helium, to the emergence of life on Earth, molecular interstellar clouds are an early link, the most primitive objects which display any significant organic chemistry. One such cloud was the direct precursor to the solar system and to all objects which it contains. Theoretical methods are ideally suited to studying interstellar cloud chemistry. They have been applied to determine spectroscopic constants of candidate interstellar molecules, mechanisms of ion-molecule reactions, and composition of dust grains. Accurate predictions of rotational constants and dipole moments of long-chain carbon molecules HC13N, HC15N, and C5O have been made to aid in determining the size limit of gas-phase interstellar molecules. Models of gas-phase interstellar chemistry use reaction rate constants measured at room temperature and extrapolated to interstellar temperatures. The temperature dependence of NH3(+)+H2 yields NH4(+)+H is anomalous, however, with a minimum rate at about 100K, casting doubt on the extrapolation procedures. The temperature dependence has now been explained.

Defrees, D. J.↗
NASA NTRS2005

Strained Hydrocarbons as Potential Hypergolic Fuels

A storable combination of high-energy hypergolic fuel and oxidizer is advantageous to the future of reusable launch vehicles (RLVs). The combination will allow an increase in energy per unit volume of fuel and eliminate the need for an external ignition system. Strained systems have been studied as potential high-density fuels. Adding hypergolic functional groups, such as amino groups, to these hydrocarbons will potentially allow auto ignition of strained systems with hydrogen peroxide. Several straight chain amines and their strained counterparts containing an equivalent number of carbon atoms have been purchased and synthesized. These amines provide initial studies to determine the effects of fuel vapor pressure, strain energy, fuel miscibility, and amine substitution upon fuel ignition time and hypergolicity with hydrogen peroxide as an oxidizer.

Source record↗
NASA NTRS2001

Catalysis in the 3rd Dimension: How Organic Molecules May be Formed

Catalysis is often little more than a word to phenomenologically describe the fact that a reaction follows a pat1 that leads to products of an unexpected kind or of unexpected yield. Low activation energy barriers for intermediates are recognized as the most likely cause why a system deviates from the thermodynamic pull towards minimizing its free energy and ends up in a metastable state. Seldom is the mechanism known. This i: particularly true for heterogeneous catalysis under hydrothermal conditions with minerals as catalysts. It is commonly assumed that catalytic action takes place across solid-fluid interfaces and that, on the atomic level, interfaces are just 2-dimensional contacts. This makes it difficult to understand, for instance, the assembly of long-chain carboxylic (fatty) acids. 3y studying single crystals that grew from a melt in the presence of H2O and CO2, we can show: (1) that numerals take up the fluid components into solid solution, (2) that some-thing happens converting them to -educedH and C, (3) that C atoms segregate into dislocations and tie C-C bonds. The products are medium-to-long chain Cn protomolecules, with some C-H attached, pre-assembled in the dislocations. Upon solvent extraction, these proto-molecules turn into carboxylic and dicarboxylic acids. This observation suggests that, in a very elementary step, catalysis under hydrothermal conditions leading to fatty acids involves the pre-assembly of Cn entities in the interface that is not 2-D but extends into the 3rd dimension, with dislocations as synthesis sites.

Freund, Friedemann↗
NASA NTRS2001

Abundances of Linear Carbon-Chain Molecules in Supernovae

This paper evaluates the condensation of carbon solids in a gas of pure C and O atoms when these exist within the interior of an expanding young supernova. We calculate the abundances of large carbon molecules, which serve as nucleations for condensation of graphites. Additional information is contained in the original extended abstract.

Clayton, D. D.↗
NASA NTRS1973

The atomic nature of polymer-metal interactions in adhesion, friction and wear

Adhesion experiments with polytetra-fluoroethylene (PTFE) and polyimide contacting tungsten indicate that the polymers bond chemically to the clean metal surface. Polymer chain fragments which transfer to the surface of tungsten in field ion microscopy adhesion studies are highly oriented. Auger emission spectroscopy of PTFE transfer films to various metal surfaces indicates that the PTFE is bonded to the metal surface via the carbon atom. With PTFE in sliding contact with different orientations of aluminum, metal orientation is found to influence surfaces in sliding. The lowest friction and least amount of surface damage is detected on the highest atomic density (111) plane. The friction process itself can initiate polymer film formation from simple organic molecules.

Buckley, D. H.↗
NASA NTRS1979

Long chain carbon molecules and diffuse interstellar lines

An estimate of the abundances of chain hydrocarbon molecules expected in dense interstellar clouds as a result of gas-phase chemistry alone supports the hypothesis that the long chain molecules are responsible for the diffuse interstellar lines seen in the optical spectra of stars lying behind fairly low-density interstellar clouds. In particular, it is shown that the equilibrium abundances of the long chain carbon molecules may remain quite high even for molecules with as many as 11 carbon atoms.

Mitchell, G. F.↗