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At least 109 records · Page 6

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NASA NTRS1987

The role of electronic mechanisms in surface erosion and glow phenomena

Experimental studies of desorption induced by electronic transitions (DIET) are described. Such studies are producing an increasingly complete picture of the dynamical pathways through which incident electronic energy is absorbed and rechanneled to produce macroscopic erosion and glow. These mechanistic studies can determine rate constants for erosion and glow processes in model materials and provide valuable guidance in materials selection and development. Extensive experiments with electron, photon, and heavy particle irradiation of alkali halides and other simple model materials have produced evidence showing that: (1) surface erosion, consisting primarily in the ejection or desorption of ground-state neutral atoms, occurs with large efficiencies for all irradiated species; (2) surface glow, resulting from the radiative decay of desorbed atoms, likewise occurs for all irradiating species; (3) the typical mechanism for ground-state neutral desorption is exciton formation, followed by relaxation to a permanent, mobile electronic defect which is the precursor to bond-breaking in the surface or near-surface bulk of the material; and (4) the mechanisms for excited atom formation may include curve crossing in atomic collisions, interactions with surface defect or impurity states, or defect diffusion.

Haglund, Richard F., Jr.↗

NASA NTRS1994

Real refractive indices of infrared-characterized nitric-acid/ice films: Implications for optical measurements of polar stratospheric clouds

The infrared spectra of nitric-acid/ice films representative of polar stratospheric clouds (PSCs) were collected with simultaneous optical interference measurements to determine the real refractive indices at lambda = 632 nm. Ice and amphorous nitric-acid/ice films were prepared by condensation of water and nitric acid vapors onto a wedged Al2O3 substrate. The real refractive indices of these films were determined from the optical interference of a reflected helium-neon laser during film growth. The indices of the amphorous films varied smoothly from n = 1.30 for ice to n = 1.49 for nitric acid, similar to observations in previous work. We were unable to obtain the refractive index of crystlline films during adsorption because of optical scattering caused by surface roughness. Therefore crystlline nitric acid hydrate films were prepared by annealing amphorous nitric-acid/ice films. Further heating caused desorption of the crystalline hydrate films. During desorption, the refractive indices for ice, NAM (nitric acid monohydrate), alpha- and beta-NAT (nitric acid trihydrate) films were measured using the optical interference technique. In agreement with earlier data, the real refractive indices for ice and NAM determined in desorption were n = 1.30 +/- 0.01 and n = 1.53 +/- 0.03, respectively. The real refractive indices for alpha- and beta-NAT were found to be n = 1.51 +/- 0.01 and n greater than or equal to 1.46, respectively. Our measurements also suggest that the shape of crystalline nitric acid particles may depend on whether they nucleate from the liquid or by vapor deposition. If confirmed by future studies, this observation may provide a means of distinguishing the nucleation mechanism of crystalline PSCs.

Middlebrook, Ann M.↗

NASA NTRS2001

Chemical and Isotopic Analysis of Trace Organic Matter on Meteorites and Interstellar Dust Using a Laser Microprobe Instrument

Polycyclic Aromatic Hydrocarbons (PAHs) are of considerable interest today because they are ubiquitous on Earth and in the interstellar medium (ISM). In fact, about 20% of cosmic carbon in the galaxy is estimated to be in the form of PAHs. Investigation of these species has obvious uses for determining the cosmochemistry of the solar system. Work in this laboratory has focused on four main areas: 1) Mapping the spatial distribution of PAHs in a variety of meteoritic samples and comparing this distribution with mineralogical features of the meteorite to determine whether a correlation exists between the two. 2) Developing a method for detection of fullerenes in extraterrestrial samples using microprobe Laser Desorption Ionization Mass Spectroscopy and utilizing this technique to investigate fullerene presence, while exploring the possibility of spatially mapping the fullerene distribution in these samples through in situ detection. 3) Investigating a possible formation pathway for meteoritic and ancient terrestrial kerogen involving the photochemical reactions of PAHs with alkanes under prebiotic and astrophysically relevant conditions. 4) Studying reaction pathways and identifying the photoproducts generated during the photochemical evolution of PAH-containing interstellar ice analogs as part of an ongoing collaboration with researchers at the Astrochemistry Lab at NASA Ames. All areas involve elucidation of the solar system formation and chemistry using microprobe Laser Desorption Laser Ionization Mass Spectrometry. A brief description of microprobe Laser Desorption Ionization Mass Spectroscopy, which allows selective investigation of subattomole levels of organic species on the surface of a sample at 10-40 micrometer spatial resolution, is given.

Zare, Richard N.↗

NASA NTRS2005

Spool Valve for Switching Air Flows Between Two Beds

U.S. Patent 6,142,151 describes a dual-bed ventilation system for a space suit, with emphasis on a multiport spool valve that switches air flows between two chemical beds that adsorb carbon dioxide and water vapor. The valve is used to alternately make the air flow through one bed while exposing the other bed to the outer-space environment to regenerate that bed through vacuum desorption of CO2 and H2O. Oxygen flowing from a supply tank is routed through a pair of periodically switched solenoid valves to drive the spool valve in a reciprocating motion. The spool valve equalizes the pressures of air in the beds and the volumes of air flowing into and out of the beds during the alternations between the adsorption and desorption phases, in such a manner that the volume of air that must be vented to outer space is half of what it would be in the absence of pressure equalization. Oxygen that has been used to actuate the spool valve in its reciprocating motion is released into the ventilation loop to replenish air lost to vacuum during the previous desorption phase of the operating cycle.

Dean, W. Clark↗

NASA NTRS2014

Cold Water Vapor in the Barnard 5 Molecular Cloud

After more than 30 yr of investigations, the nature of gas-grain interactions at low temperatures remains an unresolved issue in astrochemistry. Water ice is the dominant ice found in cold molecular clouds; however, there is only one region where cold ((is) approximately 10 K) water vapor has been detected-L1544. This study aims to shed light on ice desorption mechanisms under cold cloud conditions by expanding the sample. The clumpy distribution of methanol in dark clouds testifies to transient desorption processes at work-likely to also disrupt water ice mantles. Therefore, the Herschel HIFI instrument was used to search for cold water in a small sample of prominent methanol emission peaks. We report detections of the ground-state transition of o-H2O (J = 110-101) at 556.9360 GHz toward two positions in the cold molecular cloud, Barnard 5. The relative abundances of methanol and water gas support a desorption mechanism which disrupts the outer ice mantle layers, rather than causing complete mantle removal.

ISM: molecules↗

NASA NTRS2014

A Compact Tandem Two-Step Laser Time-of-Flight Mass Spectrometer for In Situ Analysis of Non-Volatile Organics on Planetary Surfaces

Two-step laser desorption mass spectrometry is a well suited technique to the analysis of high priority classes of organics, such as polycyclic aromatic hydrocarbons, present in complex samples. The use of decoupled desorption and ionization laser pulses allows for sensitive and selective detection of structurally intact organic species. We have recently demonstrated the implementation of this advancement in laser mass spectrometry in a compact, flight-compatible instrument that could feasibly be the centerpiece of an analytical science payload as part of a future spaceflight mission to a small body or icy moon.

time-of-flight↗

NASA NTRS1972

Measurement of single crystal surface parameters

The sticking coefficient and thermal desorption spectra of Cs from the (110) plane of W was investigated. A sticking coefficient of unity for the monolayer region was measured for T 250 K. Several distinct binding states were observed in the thermal desorption spectrum. Work function and electron reflection measurements were made on the (110) and (100) crystal faces of Mo. Both LEED and Auger were used to determine the orientation and cleanliness of the crystal surfaces. The work function values obtained for the (110) and (100) planes of Mo were 4.92 and 4.18 eV respectively.

Swanson, L. W.↗

NASA NTRS1975

Chemisorption kinetics of hydrogen on evaporated iron films

Measurements were made of the isothermal adsorption-desorption kinetics for H2 chemisorbed onto Fe films. The chemisorption process is observed to proceed via a precursor state of adsorbed molecular hydrogen similar to the H2-Ni system. The first measurements of the activation energy for desorption, and estimates of the values of the fast kinetic rates between the precursor and chemisorbed states are reported. Adsorption into the precursor state does not appear to be activated, but the process connecting the precursor state with the chemisorbed state will, under certain circumstances, be a rate limiting step for adsorption. The effects of contamination of the surface are evidenced in the measurements.

Shanabarger, M. R.↗

NASA NTRS1974

Adsorption and condensation of Cu on W single-crystal surfaces

The adsorption and condensation of Cu up to several monolayers in thickness on tungsten 110 and 100 single-crystal surfaces are studied by combining low-energy electron diffraction, Auger electron spectroscopy, thermal desorption spectroscopy, work-function measurements, and quartz microbalance thickness measurements in one experimental system. The results show drastic differences in the evolution of the structure, work function, and desorption behavior between 110 and 100 surfaces. These differences are understandable in terms of the atomic roughness of the surfaces.

Bauer, E.↗

NASA NTRS1975

Chemisorption kinetics of hydrogen on evaporated iron films

An investigation is conducted of the kinetics of isothermal adsorption-desorption processes involving molecular hydrogen which is chemisorbed onto thin (20 to 50 A) polycrystalline Fe films at temperatures near 300 K. The results of the investigation indicate that chemisorption in the H2-Fe system occurs via a precursor state of molecularly adsorbed hydrogen. Contamination of the surface from unknown impurities in the gas phase is found to affect the number of available adsorption sites and to modify the prefactor for the absolute desorption rate constant for the precursor state.

Shanabarger, M. R.↗

NASA NTRS1975

Kinetics of boron deposition by the hydrogen reduction of boron trichloride

The chemical vapor deposition of boron filament is generally considered to be limited by the diffusion of the reactive species to the hot substrate. From concentration gradient considerations and from experimental measurements it is concluded that the product species (HCl) is more likely to be involved in limiting the deposition rate. Comparison of theoretically calculated and experimentally measured deposition rates show that the rate is generally partially limited by diffusion and partially by the surface reaction rate (desorption) of HCl. The relative amounts of surface reaction or diffusion rate impedance were determined as a function of temperature and gas velocity. The temperature coefficient for the desorption of HCl was found to be 52 Kcal/mole.

Mehalso, R. M.↗

NASA NTRS1977

Evaluation of techniques for removal of spacecraft contaminants from activated carbon

Alternative techniques for the regeneration of carbon contaminated with various spacecraft contaminants were evaluated. Four different modes of regeneration were evaluated: (1) thermal desorption via vacuum, (2) thermal desorption via nitrogen purge, (3) in-situ catalytic oxidation of adsorbed contaminants, and (4) in-situ non-catalytic oxidation of adsorbed contaminants.

Mcnulty, K. J.↗

NASA NTRS1977

Mars - Photodesorption from mineral surfaces and its effects on atmospheric stability

Kinetic constraints are employed to identify the reactive chemisorbed complexes, to describe the mechanism of UV-accelerated desorption from Fe (+2) on mineral surfaces, and to estimate the photodesorption rate on Mars. In particular, it is proposed that gases such as O2, CO2, CO, H2O and N2 undergo an adsorption-desorption process at octahedrally coordinated Fe (+2) surface sites to produce seven-coordinate transition-state complexes. The ligand field stabilization energy acquired by these complexes lies between 16 and 18 kcal per mole. Published photocatalysis data are used to assess the role of photodesorption in Martian atmospheric chemistry and stability.

Huguenin, R. L.↗

NASA NTRS1979

On the kinetics of volatile loss from chondrites

Data by Lipschutz and coworkers (1975, 1976, 1977) on thermal release of Tl, Bi, and In from primitive chondrites are reexamined to obtain information on the nature and activation energy (E) of release processes: desorption, volume diffusion, and decomposition of the host phase. For the Allende C3 chondrite, the main release for Bi and Tl between 400 and 700 C is shown to be apparently due to desorption of a surface layer, coupled with grain boundary diffusion as the slow step. Further, the main release of In above 600 C and the small tails of Bi and Tl between 700 and 1000 C are observed to represent probably volume diffusion. Results for Abee and other primitive meteorites were found to be essentially similar, except for a very abrupt 500 C release of Tl from Krymka (81%) and Bi from Tieschitz (70%). It is suggested that this release may represent decomposition of a thermolabile phase in a late condensate, such as organic matter or phyllosilicates.

Alaerts, L.↗

NASA NTRS1980

The enhanced oxidation of SO2 by NO2 on carbon particulates

The oxidation of SO2 on carbon particles in dry air and in air at 65% relative humidity (RH) was found to be greatly enhanced by the presence of gaseous NO2. Exposures of 20-80ppm SO2 + 10ppm NO2 on 1-mg samples of commercial carbon black were found to produce both sorption and desorption coverages (weight retained after desorption into N2) of over one order of magnitude greater than for corresponding SO2 exposures. Significant agglomeration and wetting were observed to occur progressively during exposures at 65% RH, and samples, even after 150-h exposure, rarely reached steady-state weight gain. The wetting may have regenerated fresh reactive carbon surface. Sorptions conducted in nitrogen atmospheres, rather than in air, appeared to produce slightly higher sorptions and weight retentions for equivalent exposure concentrations and times, indicating that NO2 served as the oxidizer and that molecular oxygen, or some trace constitutents in air, may have weakly inhibited the oxidation by NO2. Wet chemical analysis of the desorbed phase indicated that sulfate, presumably H2SO4 accounted for over half of the retained weight. Measurements of pH from water-quenched samples indicated a highly acidic surface phase, and suggested the oxidation process could proceed in an acidic environment.

Cofer, W. R., III↗

NASA NTRS1980

An investigation of the kinetics for hydrogen chemisorption on iron metal surfaces

A quasi-isothermal approach was used to study the kinetics of hydrogen and hydrogen sulfide chemisorption onto iron film in an effort to understand the environmental degradation of steels. The coverage of chemisorbed hydrogen or chemisorbed sulfur was observed as a function of time for fixed conditions of substrate temperature. Auger electron spectroscopy was used to observe the sulfur and chemisorption-induced resistance change was employed to monitor hydrogen coverage. To compare the results obtained from studying the kinetics by two different techniques, the kinetics of oxygen chemisorption onto iron films was also studied. A reaction model utilized to interpret the H2/Fe2 chemisorption kinetics was applied to data from an earlier study on the desorption kinetics for H2 chemisorbed onto nicket films in the vicinity of the Curie temperature of the film. This analysis permitted a separation of the gross desorption process into individual components so that the influence of the magnetic phase transition on the rate constants could be determined.

Shanabarger, M. R.↗

NASA NTRS1982

UHV studies of the interaction of CO with small supported metal particles, Ni/mica

The interaction of carbon monoxide with small nickel (Ni) particles supported on UHV-cleaved mica was studied using flash thermal desorption, Auger electron spectroscopy, and transmission electron microscopy. Molecular desorption was accompanied by decomposition of CO at a rate strongly dependent on particle size. Recombination of surface-precipitated carbon with adsorbed oxygen was observed, and gas-induced morphological particle changes because of exposure to CO and O2 are analyzed in some detail.

Doering, D. L.↗

NASA NTRS1982

UHV studies of the interaction of CO with small supported metal particles, Pd/mica

The interaction of carbon monoxide with small palladium particles supported on UHV-cleaved and heat-treated single-crystal mica was studied. The Pd particles were characterized and tested using the techniques of flash thermal desorption, Auger electron spectroscopy, core electron energy loss spectroscopy, and transmission electron microscopy. Evidence is presented for CO decomposition on Pd particles during CO adsorption-desorption experiments. The rate of CO decomposition increased rapidly with diminishing particle size. Residual carbon from CO decomposition blocked CO adsorption and had a strong poisoning effect on the CO oxidation reaction.

Doering, D. L.↗