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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 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

2D imaging of absolute methyl concentrations in nanosecond pulsed plasma by photo-fragmentation laser-induced fluorescence

The methyl radical plays a central role in plasma-assisted hydrocarbon chemistry but is challenging to detect due to its high reactivity and strongly pre-dissociative electronically excited states. In this work, we report the development of a photo-fragmentation laser-induced fluorescence (PF-LIF) diagnostic for quantitative 2D imaging of methyl profiles in a plasma. This technique provides temporally and spatially resolved measurements of local methyl distributions, including in near-surface regions that are important for plasma-surface interactions such as plasma-assisted catalysis. The technique relies on photo-dissociation of methyl by the fifth harmonic of a Nd:YAG laser at 212.8 nm to produce CH fragments. These photofragments are then detected with LIF imaging by exciting a transition in the B-X(0, 0) band of CH with a second laser at 390 nm. Fluorescence from the overlapping A-X(0, 0), A-X(1, 1), and B-X(0, 1) bands of CH is detected near 430 nm with the A-state populated by collisional B-A electronic energy transfer. This non-resonant detection scheme enables interrogation close to a surface. The PF-LIF diagnostic is calibrated by producing a known amount of methyl through photo-dissociation of acetone vapor in a calibration gas mixture. We demonstrate PF-LIF imaging of methyl production in methane-containing nanosecond pulsed plasmas impinging on dielectric surfaces. Absolute calibration of the diagnostic is demonstrated in a diffuse, plane-to-plane discharge. Measured profiles show a relatively uniform distribution of up to 30 ppm of methyl. Relative methyl measurements in a filamentary plane-to-plane discharge and a plasma jet reveal highly localized intense production of methyl. The utility of the PF-LIF technique is further demonstrated by combining methyl measurements with formaldehyde LIF imaging to capture spatiotemporal correlations between methyl and formaldehyde, which is an important intermediate species in plasma-assisted oxidative coupling of methane.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
NASA NTRS1981

Interstellar chemistry - Polycyanoacetylene formation

It is argued that interstellar polycyanoacetylenes are formed not on dust grains by catalytic buildup or by dissociation of longer molecules, but rather by gas phase ion-molecule reactions. The primary evidence for this view is the detection of deuterated cyanoacetylene in an interstellar cloud. It is also argued that the relative abundance of successive homologs of polycyanoacetylenes rules out the grain catalysis theory.

Langer, W. D.↗
NASA NTRS1991

Spatially resolved quantitative spectroscopy of comets

The chemical composition of cometary nuclei and the velocity field of the ejected daughter species were investigated through conventional, high-resolution spectroscopy and indirectly by imaging the dissociation radicals in the outflowing cometary comae. Gas production rates and comae symmetries were studied, and coma outflow mechanisms were modeled.

Spinrad, Hyron↗
DOE OSTI2023

High reactivity of mesoporous CeO 2 to dissociate chemical warfare agent sarin

We perform spectroscopic surface characterization on mesoporous ceria (CeO 2 ) under exposure of sarin gas, also known as GB. We find mesoporous CeO 2 displays extraordinary reactivity towards GB dissociation under high vacuum. The spectroscopic results combined with density functional theory (DFT) calculations suggest that the cleavage of the P–F and P–OR bonds are both possible pathways for GB to dissociate on the CeO 2 surfaces. The modeling reveals differences in dissociation pathways of GB on the crystallographic (111)- and (110)-surfaces of ceria. Here we also report some dissociation of GB on mesoporous CeO 2 under ambient conditions. The finding that mesoporous CeO 2 can degrade GB under mild conditions is encouraging and implies the strong potential of ceria-based materials to be applied in combating chemical warfare agents related to the GB series.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Sand Migration Simulation during Gas Production from Gas Hydrate Reservoir at Kuparuk 7–11–12 site in the Prodhoe Bay Unit, Alaska

Uncontrolled sand production impedes continuous gas production from a hydrate reservoir as observed in the past field-scale gas production tests. Sand mobilization is strongly linked with sediment deformation and high pressure gradient. Sand production occurs when the mobilized sands reach the well. Throughout gas production from a hydrate reservoir, because of hydrate dissociation, deformation and pressure gradient change both in time and space. Therefore, it is necessary to consider the entire process to identify where sand is likely mobilized and how much mobilized sand could reach the well. Here, this study utilizes a coupled thermal, hydrological, chemical, and mechanical (thermo-hydro-chemo-mechanical) sand migration model to simulate a year long gas production from the hydrate reservoir at the Kuparuk 7–11–12 site in the Prodhoe Bay Unit, Alaska. It is found that sand would mainly come from the lower portion of the production zone where faster hydrate dissociation occurs. The relatively faster hydrate dissociation coupled with the fact that hydrate-bearing sediments and hydrate-free sediments have similar stiffness but different strengths causes complex stress transfer, which results in excessive shear deformation when the upper portion of the production zone starts to dissociate. This is evident not only near the well but also away from the well, leading to a large amount of sand mobilization. Another focus of the modeling study is evaluation of the effect of sand migration on gas production. The comparison of two extreme cases–with sandscreen and without sandscreen–suggests that migrated and settled solids around a sand control device can prevent pressure drop across the near-wellbore zone and lead to reduction of the gas production rate.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1987

The study of excited oxygen molecule gas species production and quenching on thermal protection system materials

The detection of excited oxygen and ozone molecules formed by surface catalyzed oxygen atom recombination and reaction was investigated by laser induced fluorescence (LIF), molecular beam mass spectrometric (MBMS), and field ionization (FI) techniques. The experiment used partially dissociated oxygen flows from a microwave discharge at pressures in the range from 60 to 400 Pa or from an inductively coupled RF discharge at atmospheric pressure. The catalyst materials investigated were nickel and the reaction cured glass coating used for Space Shuttle reusable surface insulation tiles. Nonradiative loss processes for the laser excited states makes LIF detection of O2 difficult such that formation of excited oxygen molecules could not be detected in the flow from the microwave discharge or in the gaseous products of atom loss on nickel. MBMS experiments showed that ozone was a product of heterogeneous O atom loss on nickel and tile surfaces at low temperatures and that ozone is lost on these materials at elevated temperatures. FI was separately investigated as a method by which excited oxygen molecules may be conveniently detected. Partial O2 dissociation decreases the current produced by FI of the gas.

Nordine, Paul C.↗
DOE OSTI2019

Charge Movement and Structural Changes in the Gas-Phase Unfolding of Multimeric Protein Complexes Captured by Native Top-Down Mass Spectrometry

The extent to which noncovalent protein complexes retain native structure in the gas phase is highly dependent on experimental conditions. Energetic collisions with background gas can cause structural changes ranging from unfolding to subunit dissociation. Additionally, recent studies have highlighted the role of charge in such structural changes, but the mechanism is not completely understood. In this study, native top down (native TD) mass spectrometry was used to probe gas-phase structural changes of alcohol dehydrogenase (ADH, 4mer) under varying degrees of in-source activation. Changes in covalent backbone fragments produced by electron capture dissociation (ECD) or 193 nm ultraviolet photodissociation (UVPD) were correlated to structural changes of the ADH 4mer. ECD fragments indicated unfolding started at the N-terminus, and the charge states of UVPD fragments enabled monitoring of charge migration to the unfolded regions. Interestingly, UVPD fragments also indicated that the charge at the “unfolding” N-terminus of ADH decreased at high in-source activation energies after the initial increase. We proposed a possible “refolding-after-unfolding” mechanism, as further supported by monitoring hydrogen elimination from radical a-ions produced by UVPD at the N-terminus of ADH. However, “refolding-after-unfolding” with increasing in-source activation was not observed for charge-reduced ADH, which likely adopted compact structures that are resistant to both charge migration and unfolding. Combined, these results support a charge-directed unfolding mechanism for protein complexes. Overall, an experimental framework was outlined for utilizing native TD to generate structure-informative mass spectral signatures for protein complexes that complement other structure characterization techniques, such as ion mobility spectrometry and computational modeling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Sintering Mechanism of Pt/Al 2 O 3 in Complex Emission Gases Elucidated via In Situ Environmental STEM

Emission control catalysts are crucial for protecting human health by preventing the release of harmful gases and unburnt fuel into the atmosphere. These catalysts often face deactivation through sintering processes in high-temperature, chemically reactive environments containing multiple gas species. Here, we use in situ environmental scanning transmission electron microscopy to monitor the sintering behavior and transient morphologies of Pt/Al 2 O 3 in various relevant gas environments through controlled experiments. Our results reveal the particle migration and atomic ripening behavior of Pt/Al 2 O 3 at the atomic scale in the presence of water vapor and oxygen, which differs from behaviors observed in single gas environments. We identify an atomic ripening mechanism involving the dissociation and migration of Pt adatom chains from Pt nanoparticles, observed only in combinational gases. Finally, these findings provide valuable insights into catalyst degradation behavior in complex gas environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2013

Photo-Induced Deuterium Enrichment in Residues Produced from the UV Irradiation of Pyrimidine in H2O and H2O+NH3 Ices

Organic compounds found in meteorites often show isotopic signatures of their interstellar/protosolar heritage as enrichments in D and 15N. Meteoritic organics found to be enriched in D include amino acids, hydroxy and dicarboxylic acids, as well as polycyclic aromatic hydrocarbons (PAHs). Processes that can produce isotopic enrichments in presolar/protosolar materials include gas-phase ion-molecule reactions, gas-grain surface reactions, and unimolecular photo-dissociation reactions involving PAHs. Because many molecules in interstellar clouds are enriched in D, the presence of D anomalies in meteorites is thought to originate from preserved or slightly altered interstellar/protostellar materials. However, the link between isotopic enrichments seen in space and those in meteoritic compounds and their relationship remain unclear. In this work, we present results of hydrogen isotopic fractionation for compounds in organic residues produced from the UV irradiation using an H2- discharge UV lamp of H2O:pyrimidine = 20:1 and H2O:NH3:pyrimidine = 20:2:1 ice mixtures at low temperature (is less than 20 K). After irradiation, the resulting residues are dissolved in H2O and analyzed with gas chromatography-mass spectrometry coupled with isotope ratio mass spectrometry (GC-MS/IRMS) [1], following a protocol similar to that used for previous analyses of comparable samples [2,3]. We used this technique to measure compound-specific D/H isotopic ratios for the initial pyrimidine and for two photo-products present in the residues, namely, 2,2'-bipyrimidine and an unidentified bipyrimidine isomer [2-4]. Measuring D enrichments in bipyrimidines has the advantage that the H atoms on these molecules are not easily exchangeable with other compounds, in particular the H2O and NH3 present in the ices or the solvents used to extract the samples for GC-MS/IRMS measurements. The δD value for the initial pyrimidine, measured with a high-temperature conversion elemental analyzer connected to the IRMS, was found to be -30% per mille. Preliminary measurements made on a residue produced from the UV irradiation of an H2O:NH3:pyrimidine = 20:2:1 ice mixture indicate δD values of +118% per mille for 2,2'- bipyrimidine and +92% per mille for the other bipyrimidine isomer, and therefore show a significant D enrichment during the photo-processing and warm-up that lead to their formation [5]. New measurements are currently being performed on a number of residues produced from simpler H2O:pyrimidine = 20:1 ice mixtures under different experimental conditions and will be presented here.

Laboratory Astrochemistry↗
DOE OSTI2023

Multiple emission components in the Cygnus cocoon detected from Fermi -LAT observations

Star-forming regions may play an important role in the life cycle of Galactic cosmic rays (CRs), notably as home to specific acceleration mechanisms and transport conditions. Gamma-ray observations of Cygnus X have revealed the presence of an excess of hard-spectrum gamma-ray emission, possibly related to a cocoon of freshly accelerated particles. We seek an improved description of the gamma-ray emission from the cocoon using ~13 yr of observations with the Fermi-Large Area Telescope (LAT) and use it to further constrain the processes and objects responsible for the young CR population. We developed an emission model for a large region of interest, including a description of interstellar emission from the background population of CRs and recent models for other gamma-ray sources in the field. Thus, we performed an improved spectro-morphological characterisation of the residual emission including the cocoon. The best-fit model for the cocoon includes two main emission components: an extended component FCES G78.74+1.56, described by a 2D Gaussian of extension r 68 = 4.4° ± 0.1° -0.1° +0.1° and a smooth broken power law spectrum with spectral indices 1.67 ± 0.05 -0.01 +0.02 and 2.12 ± 0.02 -0.01 +0.00 below and above 3.0 ± 0.6 -0.2 +0.0 GeV, respectively; and a central component FCES G80.00+0.50, traced by the distribution of ionised gas within the borders of the photo-dissociation regions and with a power law spectrum of index 2.19 ± 0.03 -0.01 +0.00 that is significantly different from the spectrum of FCES G78.74+1.56. An additional extended emission component FCES G78.83+3.57, located on the edge of the central cavities in Cygnus X and with a spectrum compatible with that of FCES G80.00+0.50, is likely related to the cocoon. For the two brightest components FCES G80.00+0.50 and FCES G78.74+1.56, spectra and radial-azimuthal profiles of the emission can be accounted for in a diffusion-loss framework involving one single population of non-thermal particles with a flat injection spectrum. Particles span the full extent of FCES G78.74+1.56 as a result of diffusion from a central source, and give rise to source FCES G80.00+0.50 by interacting with ionised gas in the innermost region. For this simple diffusion-loss model, viable setups can be very different in terms of energetics, transport conditions, and timescales involved, and both hadronic and leptonic scenarios are possible. The solutions range from long-lasting particle acceleration, possibly in prominent star clusters such as Cyg OB2 and NGC 6910, to a more recent and short-lived release of particles within the last 10–100 kyr, likely from a supernova remnant. The observables extracted from our analysis can be used to perform detailed comparisons with advanced models of particle acceleration and transport in star-forming regions.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS2006

Generating Breathable Air Through Dissociation of N2O

A nitrous oxide-based oxygen-supply system (NOBOSS) is an apparatus in which a breathable mixture comprising 2/3 volume parts of N2 and 1/3 volume part of O2 is generated through dissociation of N2O. The NOBOSS concept can be adapted to a variety of applications in which there are requirements for relatively compact, lightweight systems to supply breathable air. These could include air-supply systems for firefighters, divers, astronauts, and workers who must be protected against biological and chemical hazards. A NOBOSS stands in contrast to compressed-gas and cryogenic air-supply systems. Compressed-gas systems necessarily include massive tanks that can hold only relatively small amounts of gases. Alternatively, gases can be stored compactly in greater quantities and at low pressures when they are liquefied, but then cryogenic equipment is needed to maintain them in liquid form. Overcoming the disadvantages of both compressed-gas and cryogenic systems, the NOBOSS exploits the fact that N2O can be stored in liquid form at room temperature and moderate pressure. The mass of N2O that can be stored in a tank of a given mass is about 20 times the mass of compressed air that can be stored in a tank of equal mass. In a NOBOSS, N2O is exothermically dissociated to N2 and O2 in a main catalytic reactor. In order to ensure the dissociation of N2O to the maximum possible extent, the temperature of the reactor must be kept above 400 C. At the same time, to minimize concentrations of nitrogen oxides (which are toxic), it is necessary to keep the reactor temperature at or below 540 C. To keep the temperature within the required range throughout the reactor and, in particular, to prevent the formation of hot spots that would be generated by local concentrations of the exothermic dissociation reaction, the N2O is introduced into the reactor through an injector tube that features carefully spaced holes to distribute the input flow of N2O widely throughout the reactor. A NOBOSS includes one or more "destroyer" subsystems for removing any nitrogen oxides that remain downstream of the main N2O-dissociation reactor. A destroyer includes a carbon bed in series with a catalytic reactor, and is in thermal contact with the main N2O-dissociation reactor. The gas mixture that leaves the main reactor first goes through a carbon bed, which adsorbs all of the trace NO and most of the trace NO2. The gas mixture then goes through the destroyer catalytic reactor, wherein most or all of the remaining NO2 is dissociated. A NOBOSS can be designed to regulate its reactor temperature across a range of flow rates. One such system includes three destroyer loops; these loops act, in combination with a heat sink, to remove heat from the main N2O-dissociation reactor. In this system, the N2O and product gases play an additional role as coolants; thus, as needed, the coolant flow increases in proportion to the rate of generation of heat, helping to keep the main-reactor temperature below 540 C.

Zubrin, Robert↗
NASA NTRS1959

Theoretical and Experimental Investigation of Heat Conduction in Air, Including Effects of Oxygen Dissociation

Solutions are presented for the conduction of beat through a semi-infinite gas medium having a uniform initial temperature and a constant boundary temperature. The coefficients of thermal conductivity and diffusivity are treated as variables, and the solutions are extended to the case of air at temperatures where oxygen dissociation occurs. These solutions are used together with shock-tube measurements to evaluate the integral of thermal conductivity for air as a function of temperature.

Hansen, C. Frederick↗
NASA NTRS1979

Molecule formation and infrared emission in fast interstellar shocks. I Physical processes

The paper analyzes the structure of fast shocks incident upon interstellar gas of ambient density from 10 to the 7th per cu cm, while focusing on the problems of formation and destruction of molecules and infrared emission in the cooling, neutral post shock gas. It is noted that such fast shocks initially dissociate almost all preexisting molecules. Discussion covers the physical processes which determine the post shock structure between 10 to the 4 and 10 to the 2 K. It is shown that the chemistry of important molecular coolants H2, CO, OH, and H2O, as well as HD and CH, is reduced to a relatively small set of gas phase and grain surface reactions. Also, the chemistry follows the slow conversion of atomic hydrogen into H2, which primarily occurs on grain surfaces. The dependence of this H2 formation rate on grain and gas temperatures is examined and the survival of grains behind fast shocks is discussed. Post shock heating and cooling rates are calculated and an appropriate, analytic, universal cooling function is developed for molecules other than hydrogen which includes opacities from both the dust and the lines.

Hollenbach, D.↗
NASA NTRS1974

Use of hexafluoroethane to simulate the inviscid real-gas effects on blunt entry vehicles

Results are presented of an experimental and theoretical investigation of the use of equilibrium hexafluoroethane C2F6 as an undissociated test gas in a wind tunnel to simulate the inviscid aerodynamic characteristics of blunt bodies in high-speed flight where dissociation occurs. The results indicate that the use of C2F6 as a test gas in wind tunnels is a practical and relatively simple and inexpensive method of obtaining test conditions with large normal-shock density ratios. Equations for the thermodynamic and transport properties of C2F6 are also included.

Hunt, J. L.↗
DOE OSTI2020

Plasma decay in hydrocarbons and hydrocarbon- and H 2 O-containing mixtures excited by high-voltage nanosecond discharge at elevated gas temperatures

Plasma decay after a high-voltage nanosecond discharge was experimentally and numerically studied in pure hydrocarbons (C 2 H 6 and C 3 H 8 ), and H 2 O:N 2 and C 3 H 8 :O 2 mixtures for pressures in the range 2–4 Torr and gas temperatures from 300 to 600 K. In a stoichiometric C 3 H 8 :O 2 mixture, plasma decay was also studied in a repetitively pulsed discharge for varing numbers of discharge pulses (varying degrees of fuel oxidation). The rate of plasma decay was determined from the temporal evolution of electron density measured using the microwave interferometer. It was observed that gas heating to 600 K leads to a decrease in the rate of plasma decay in all cases. The effect of heating on plasma decay was most profound in the H 2 O:N 2 mixture (after a single discharge pulse) and in the C 3 H 8 :O 2 mixture for high degrees of fuel oxidation. A kinetic scheme was developed to numerically simulate the plasma decay in hydrocarbons and combustible mixtures. Numerical analysis showed that, under the conditions studied, plasma decay was controlled by dissociative electron recombination with simple molecular and cluster ions. Gas heating led to a decrease in the rate of the electron-ion recombination and the rate of conversion of molecular ions to cluster ions. As a result, the gas temperature increase caused a decrease in the fraction of cluster ions for which the recombination coefficients are an order of magnitude higher than the recombination coefficients for molecular ions. The influence of gas heating on the decrease of the amount of cluster ions was more important when the ion composition was dominated by hydrated H 3 O + (H 2 O) k ions. The rates of the formation of these ions are extremely sensitive to any variations in gas temperature. A result, in agreement with our observations, gas heating led to an anomalous decrease in the rates of plasma decay in the H 2 O:N 2 mixture, as well as in the C 3 H 8 :O 2 mixture when H 2 O molecules were produced due to fuel oxidation.

20 FOSSIL-FUELED POWER PLANTS↗