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All sourcesNASA NTRSDOE OSTI
NASA NTRS1997

Continuing Studies in Support of Ultraviolet Observations of Planetary Atmospheres

This program was a one-year extension of an earlier Planetary Atmospheres program grant, covering the period 1 August 1996 through 30 September 1997. The grant was for supporting work to complement an active program observing planetary atmospheres with Earth-orbital telescopes, principally the Hubble Space Telescope (HST). The recent concentration of this work has been on HST observations of Jupiter's upper atmosphere and aurora, but it has also included observations of Io, serendipitous observations of asteroids, and observations of the velocity structure in the interplanetary medium. The observations of Jupiter have been at vacuum ultraviolet wavelengths, including imaging and spectroscopy of the auroral and airglow emissions. The most recent HST observations have been at the same time as in situ measurements made by the Galileo orbiter instruments, as reflected in the meeting presentations listed below. Concentrated efforts have been applied in this year to the following projects: The analysis of HST WFPC 2 images of Jupiter's aurora, including the Io footprint emissions. We have performed a comparative analysis of the lo footprint locations with two magnetic field models, studied the statistical properties of the apparent dawn auroral storms on Jupiter, and found various other repeated patterns in Jupiter's aurora. Analysis and modeling of airglow and auroral Ly alpha emission line profiles from Jupiter. This has included modeling the aurora] line profiles, including the energy degradation of precipitating charged particles and radiative transfer of the emerging emissions. Jupiter's auroral emission line profile is self-absorbed, since it is produced by an internal source, and the resulting emission with a deep central absorption from the overlying atmosphere permits modeling of the depth of the emissions, plus the motion of the emitting layer with respect to the overlying atmospheric column from the observed Doppler shift of the central absorption. By contrast the airglow emission line, which is dominated by resonant scattering of solar emission, has no central absorption, but displays rapid time variations and broad wings, indicative of a superthermal component (or corona) in Jupiter's upper atmosphere. Modeling of the observed motions of the plumes produced after the impacts of the fragments of Comet S/L-9 with Jupiter in July 1994, from the HST WFPC 2 imaging series.

Clark, John↗
NASA NTRS1994

XPS analysis of 440C steel surfaces lubricated with perfluoropolyethers under sliding conditions in high vacuum

This work presents the results of the X-Ray Photoelectron Spectroscopy (XPS) analysis of AISI 440C ball surfaces lubricated with perfluoropolyether (PFPE) oils after friction experiments under sliding conditions at high load in air and vacuum environments. The PFPE lubricants tested were Demnum S100, Fomblin Z-25, and Krytox 143AB. It was found that all the PFPE lubricants were degraded by sliding contact causing the formation of inorganic fluorides on the metallic surfaces and a layer of organic decomposition products. KRYTOX 143AB was the least reactive of the three lubricants tested. It was also found that metal fluoride formed at off-scar areas. This suggests the formation of reactive species, such as COF2 or R(sub f)COF, during sliding experiments, which can diffuse through the lubricant film and react with the metallic surfaces away from the contact region. Comparison of reference specimens before sliding with those that had undergone the sliding tests showed that the amount of non-degraded PFPE remaining on the surface of the balls after the sliding experiments was greater than that of the balls without sliding.

Herrera-Fierro, Pilar↗
NASA NTRS1998

Properties Data for Adhesion and Surface Chemistry of Aluminum: Sapphire-Aluminum, Single-Crystal Couple

An investigation was conducted to examine the adhesion and surface chemistry of single-crystal aluminum in contact with single-crystal sapphire (alumina). Pull-off force (adhesion) measurements were conducted under loads of 0. I to I mN in a vacuum of 10(exp -1) to 10(exp -9) Pa (approx. 10(exp -10) to 10(exp -11) torr) at room temperature. An Auger electron spectroscopy analyzer incorporated directly into an adhesion-measuring vacuum system was primarily used to define the chemical nature of the surfaces before and after adhesion measurements. The surfaces were cleaned by argon ion sputtering. With a clean aluminum-clean -sapphire couple the mean value and standard deviation of pull-off forces required to separate the surfaces were 3015 and 298 micro-N, respectively. With a contaminated aluminum-clean sapphire couple these values were 231 and 241 micro-N. The presence of a contaminant film on the aluminum surface reduced adhesion by a factor of 13. Therefore, surfaces cleanliness, particularly aluminum cleanliness, played an important role in the adhesion of the aluminum-sapphire couples. Pressures on the order of 10(exp -8) to 10(exp -9) Pa (approx. 10(exp -10) to 10(exp -11) torr) maintained a clean aluminum surface for only a short time (less then 1 hr) but maintained a clean sapphire surface, once it was achieved, for a much longer time.

Miyoshi, Kazuhisa↗
NASA NTRS1989

Degradation and crosslinking of perfluoroalkyl polyethers under X-ray irradiation in ultrahigh vacuum

Degradation of three types of commercially available perfluoroalkyl polyethers (PFPE)-Demnum S200, Fomblin Z25, and Krytox 16256-by X-ray irradiation was studied by using X-ray photoemission spectroscopy (XPS) and a mass spectrometer under ultra-high-vacuum conditions. The carbons in the polymers were characterized by chemical shifts of Cls binding energies. Gaseous products containing COF2 and low-molecular-weight fluorocarbons were formed. From Fomblin Z25, which has acetal linkages (-OCF2O-), a large quantity of COF2 gas was evolved. Liquid products became tacky after a long irradiation time, and some did not dissolve in Freon. High-pressure liquid chromatography (HPLC) showed that molecular weight distribution became broader and that higher molecular weight polymers were formed from Demnum and Krytox. We concluded from these results that degradation and cross-linking took place simultaneously. Demnum crosslinked more easily than the other fluids. The time dependence of both XPS spectra of Cls and mass spectra showed that C-O-bonded carbons in PFPE'S were removed faster than other carbons. There was no substrate effect on the degradation reaction because the first-order rate constants calculated from the change of gaseous products were similar when stainless steel (440C) and gold-coated surfaces were used. Metal fluorides were formed on stainless steel during the reaction. A mechanism for the degradation of PFPE'S is discussed on the basis of their molecular structures.

Mori, Shigeyuki↗
NASA NTRS1998

"Un-annealed and Annealed Pd Ultra-Thin Film on SiC Characterized by Scanning Probe Microscopy and X-ray Photoelectron Spectroscopy"

Pd/SiC has been used as a hydrogen and a hydrocarbon gas sensor operated at high temperature. UHV (Ultra High Vacuum)-Scanning Tunneling Microscopy (STM), Atomic Force Microscopy (AFM) and X-ray Photoelectron Spectroscopy (XPS) techniques were applied to study the relationship between the morphology and chemical compositions for Pd ultra-thin films on SiC (less than 30 angstroms) at different annealing temperatures. Pd ultra-thin film on 6H-SiC was prepared by the RF sputtering method. The morphology from UHV-STM and AFM shows that the Pd thin film was well deposited on SiC substrate, and the Pd was partially aggregated to round shaped participates at an annealing temperature of 300 C. At 400 C, the amount of surface participates decreases, and some strap shape participates appear. From XPS, Pd2Si was formed on the surface after annealing at 300 C, and all Pd reacted with SiC to form Pd2Si after annealing at 400 C. The intensity of the XPS Pd peak decreases enormously at 400 C. The Pd film diffused into SiC, and the Schottky barrier height has almost no changes. The work shows the Pd sicilides/SiC have the same electronic properties with Pd/SiC, and explains why the Pd/SiC sensor still responds to hydrogen at high operating temperatures.

Lu, W. J.↗
NASA NTRS1999

Determination of Spectroscopic Properties of Atmospheric Molecules from High Resolution Vacuum Ultraviolet Cross Section and Wavelength Measurements

We have studied the spectroscopy and the cross sections of the simple molecules of atmospheric interest such as oxygen, nitric oxide, carbon dioxide, and water. We have made cross section measurements on an absolute base without the effects from the limited instrumental resolution. We have used the following different instruments- the grating spectrometer (6.65-m at CfA, 3-m at Photon Factory), VUV Fourier transform spectrometer at Imperial College, and then moved the same one to the Photon Factory. Selection of the instruments depend on the appearance of molecular bands, and their wavelength region. For example, the cross section measurements of Doppler limited bands can been done with the Fourier transform spectrometer at the very high resolution (0.025/ cm resolution). All of these spectroscopic measurements are needed for accurate calculations of the production of atomic oxygen penetration of solar radiation into the Earth's atmosphere, and photochemistry of minor molecules.

Parkinson, W. H.↗
NASA NTRS1990

X-ray photoelectron spectroscopy peak assignment for perfluoropolyether oils

Perfluoroalkylpolyether (PFPE) oils are increasingly being used as vacuum pump oils and as lubricants for magnetic recording media and instrumentation for satellites. In this paper, the relative binding energies of three PFPE oils are determined. When sample oils are continuously irradiated during X-ray spectroscopy (XPS) measurements, the relative peak intensity of the spectra is altered significantly, indicating that gaseous products form from the oils during XPS measurements. Thus, attention should be paid to chemical changes when XPE is used to characterize fluorinated carbons such as PFPE oils.

Mori, Shigeyuki↗
NASA NTRS1981

X-ray photoemission studies of superficially oxidized cesium antimonide photoemitters

Superficially oxidized cesium antimonide photoemitting surfaces prepared in ultrahigh vacuum were studied by X-ray photoelectron spectroscopy. Oxidation of Cs3Sb to produce a surface with enhanced photosensitivity converts part of the antimony to elemental antimony and part of the cesium to cesium suboxide. The latter is identified on the basis of an O1 s peak at 531.3 eV, characteristic of Cs11O3. The production of Cs2O is not ruled out in this process since its signature at 527.5 eV is masked by an antimony shake-up peak at 527 eV.

Bates, C. W., Jr.↗
NASA NTRS1984

Effect of ion sputtering on interface chemistry and electrical properties of Au GaAs(100) Schottky contacts

The effects of sputtering n-type (100)GaAs with 1 to 5 keV argon ions have been studied in ultrahigh vacuum. Auger electron and X-ray photoelectron spectroscopies have been used to characterize the surface before and after sputtering. Gold Schottky contacts were prepared in situ to avoid contamination at the metal/semiconductor interface. The data show that sputtering depletes the surface in As, and the extent of depletion increased as the ion energy was increased. However, angular-resolved photoelectron data showed As was enriched on the outer atom layer by 5 keV but depleted by 1 keV Ar(+) sputtering. Current and capacitance versus voltage data showed that sputtering always lowered the Schottky barrier height and generally increased the ideality factor. However, the barrier height after 3 keV sputtering was higher than after 1 keV sputtering. Those effects are explained based on a combined effective work function model and creation of a donorlike surface damage layer. The donor layer was correlated with As depletion by sputtering. Deep level trap formation and annealing of sputtering effects were studied.

Wang, Y.-X.↗
NASA NTRS1993

XPS analysis of the effect of fillers on PTFE transfer film development in sliding contacts

The development of transfer films atop steel counterfaces in contact with unfilled and bronze-filled PTFE has been studied using X-ray photoelectron spectroscopy. The sliding apparatus was contained within the vacuum of the analytical system, so the effects of the native oxide, hydrocarbon, and adsorbed gaseous surface layers of the steel upon the PTFE transfer behavior could be studied in situ. For both the filled and the unfilled PTFE, cleaner surfaces promoted greater amounts of transfer. Metal fluorides, which formed at the transfer film/counterface interface, were found solely in cases where the native oxide had been removed to expose the metallic surface prior to sliding. These fluorides also were found at clean metal/PTFE interfaces formed in the absence of frictional contact. A fraction of these fluorides resulted from irradiation damage inherent in XPS analysis. PTFE transfer films were found to build up with repeated sliding passes, by a process in which strands of transfer filled in the remaining counterface area. Under these reported test conditions, the transfer process is not expected to continue atop previously deposited transfer films. The bronze-filled composite generated greater amounts of transfer than the unfilled PTFE. The results are discussed relative to the observed increase in wear resistance imparted to PTFE by a broad range of inorganic fillers.

Blanchet, T. A.↗
NASA NTRS2004

Analysis of He I 1083 nm Imaging Spectroscopy Using a Spectral Standard

We develop a technique. for the analysis of He I 1083 nanometer spectra which addresses several difficulties through determination of a continuum background by comparison with a well calibrated standard and through removal of nearby solar and telluric blends by differential comparison to an average spectrum. The method is compared with earlier analysis of imaging spectroscopy obtained at the National Solar Observatory/Kitt Peak Vacuum Telescope (NSO/KPVT) with the NASA/NSO Spectromagnetograph (SPM). We examine distributions of Doppler velocity and line width as a function of central intensity for an active region, filament, quiet Sun, and coronal hole. For our example, we find that line widths and central intensity are oppositely correlated in a coronal hole and quiet Sun. Line widths are comparable to the quiet sun in the active region, are systematically lower in the filament, and extend to higher values in the coronal hole. Outward velocities of approximately equal to 2 to 4 kilometers per second are typically observed in the coronal hole. The sensitivity of these results to analysis technique is discussed.

Malanushenko, Elena V.↗
NASA NTRS1990

Characterization of the surfaces of platinum/tin oxide based catalysts by Fourier Transform Infrared Spectroscopy (FTIR)

A Pt/SnO2 catalyst has been developed at NASA Langley that is effective for the oxidation of CO at room temperature (1). A mechanism has been proposed to explain the effectiveness of this catalyst (2), but most of the species involved in this mechanism have not been observed under actual catalytic conditions. A number of these species are potentially detectable by Fourier Transform Infrared Spectroscopy (FTIR), e.g., HOSnO sub x, HO sub y PtO sub z, Pt-CO, and SnHCO3. Therefore a preliminary investigation was conducted to determine what might be learned about this particular catalyst by transmission FTIR. The main advantage of FTIR for this work is that the catalyst can be examined under conditions similar to the actual catalytic conditions. This can be of critical importance since some surface species may exist only when the reaction gases are present. Another advantage of the infrared approach is that since vibrations are probed, subtle chemical details may be obtained. The main disadvantage of this approach is that FTIR is not nearly as sensitive as the Ultra High Vacuum (UHV) surface analytical techniques such as Auger, Electron Spectroscopy for Chemical Analysis (ESCA), Electron Energy Loss Spectroscopy (EELS), etc. Another problem is that the assignment of the observed infrared bands may be difficult.

Keiser, Joseph T.↗
NASA NTRS1972

Adhesion and transfer of polytetrafluorethylene to metals studied by Auger emission spectroscopy

The adhesion and transfer of polytetrafluoroethylene (PTFE) to metals in ultrahigh vacuum were studied. The transfer was effected both by compressive static contact and by sliding contact. The transfer observed after static contact was independent of the chemical constitution of the substrate. Electron-induced desorption of the fluorine in the transferred PTFE showed that the fluorine had no chemical interaction with the metal substrate. The coefficient of friction on metals was independent of the chemical constitution of the substrate. However, sliding PTFE on soft metals, such as aluminum, generated wear fragments that lodged in the PTFE and machined the substrate.

Pepper, S. V.↗
NASA NTRS2000

Laboratory investigation of the contribution of complex aromatic/aliphatic polycyclic hybrid molecular structures to interstellar ultraviolet extinction and infrared emission

We have demonstrated by experiment that, in an energetic environment, a simple polycyclic aromatic hydrocarbon (PAH) such as naphthalene will undergo chemical reactions that produce a wide array of more complex species (an aggregate). For a stellar wind of a highly evolved star (post-asymptotic giant branch [post-AGB]), this process would be in addition to what is expected from reactions occurring under thermodynamic equilibrium. A surprising result of that work was that produced in substantial abundance are hydrogenated forms that are hybrids of polycyclic aromatic and polycyclic alkanes. Infrared spectroscopy described here reveals a spectral character for these materials that has much in common with that observed for the constituents of circumstellar clouds of post-AGB stars. It can be demonstrated that a methylene (-CH2-) substructure, as in cycloalkanes, is the likely carrier of the 6.9 microns band emission of dust that has recently been formed around IRAS 22272+5433, NGC 7027, and CPD -56 8032. Ultraviolet spectroscopy previously done with a lower limit of 190 nm had revealed that this molecular aggregate can contribute to the interstellar extinction feature at 2175 angstroms. We have now extended our UV spectroscopy of these materials to 110 nm by a vacuum ultraviolet technique. That work, described here, reveals new spectral characteristics and describes how material newly formed during the late stages of stellar evolution could have produced an extinction feature claimed to exist at 1700 angstroms in the spectrum of HD 145502 and also how the newly formed hydrocarbon material would be transformed/aged in the general interstellar environment. The contribution of this molecular aggregate to the rise in interstellar extinction at wavelengths below 1500 angstroms is also examined. The panspectral measurements of the materials produced in the laboratory, using plasmas of H, He, N, and O to convert the simple PAH naphthalene to an aggregate of complex species, provide insight into possible molecular structure details of newly formed hydrocarbon-rich interstellar dust and its transformation into aged material that becomes resident in the interstellar medium. Specifically the presence of naphthalene-like and butadiene-like conjugated structures as chromophores for the 2175 angstroms ultraviolet extinction feature is indicated.

NASA Discipline Exobiology↗
NASA NTRS2008

Adsorption of Water on JSC-1A Lunar Simulant Samples

Remote sensing probes sent to the moon in the 1990s indicated that water may exist in areas such as the bottoms of deep, permanently shadowed craters at the lunar poles, buried under regolith. Water is of paramount importance for any lunar exploration and colonization project which would require self-sustainable systems. Therefore, investigating the interaction of water with lunar regolith is pertinent to future exploration. The lunar environment can be approximated in ultra-high vacuum systems such as those used in thermal desorption spectroscopy (TDS). Questions about water dissociation, surface wetting, degree of crystallization, details of water-ice transitions, and cluster formation kinetics can be addressed by TDS. Lunar regolith specimens collected during the Apollo missions are still available though precious, so testing with simulant is required before applying to use lunar regolith samples. Hence, we used for these studies JSC-1a, mostly an aluminosilicate glass and basaltic material containing substantial amounts of plagioclase, some olivine and traces of other minerals. Objectives of this project include: 1) Manufacturing samples using as little raw material as possible, allowing the use of surface chemistry and kinetics tools to determine the feasibility of parallel studies on regolith, and 2) Characterizing the adsorption kinetics of water on the regolith simulant. This has implications for the probability of finding water on the moon and, if present, for recovery techniques. For condensed water films, complex TDS data were obtained containing multiple features, which are related to subtle rearrangements of the water adlayer. Results from JSC-1a TDS studies indicate: 1) Water dissociation on JSC-1a at low exposures, with features detected at temperatures as high as 450 K and 2) The formation of 3D water clusters and a rather porous condensed water film. It appears plausible that the sub- m sized particles act as nucleation centers.

Goering, John↗
NASA NTRS1995

The effect of simulated low earth orbit radiation on polyimides (UV degradation study)

UV degradation of polyimide films in air and vacuum were studied using UV-visible, ESR, FTIR, and XPS spectroscopies. The UV-visible spectra of polyimide films showed a blue shift in the absorption compared to Kapton. This behavior was attributed to the presence of bulky groups and kinks along the polymer chains which disrupt the formation of a charge transfer complex. The UV-visible spectra showed also that UV irradiation of polyimides result extensively in surface degradation, leaving the bulk of the polymer intact. ESR spectra of polyimides irradiated in vacuum revealed the formation of stable carbon-centered radicals which give a singlet ESR spectrum, while polyimides irradiated in air produced an asymmetric signal shifted to a lower magnetic field, with a higher g value and line width. This signal was attributed to oxygen-cenetered radicals of peroxy and/or alkoxy type. The rate of radical formation in air was two fold higher than for vacuum irradiation, and reached a plateau after a short time. This suggests a continuous depletion of radicals on the surface via an ablative degradation process. FTIR, XPS, and weight loss studies supported this postulate. An XPS study of the surface indicated a substantial increase in the surface oxidation after irradiation in air. The sharp increase in the C-O binding energy peak relative to the C-C peak was believed to be associated with an aromatic ring opening reaction.

Forsythe, John S.↗
NASA NTRS1981

Tribological properties and surface chemistry of silicon carbide at temperatures to 1500 C

Silicon carbide surfaces were heated to 1500 C in a vacuum and analyzed at room temperature with X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). The basic unit of the surfaces was considered as a plane of a tetrahedron of either SiC4 and CSi4 composition. AES spectra were obtained from 250-1500 C, with an analysis depth of 1 nm revealed the presence of little Si and mostly graphite. XPS analysis depth was 2 nm or less, and Si was found in the second 1 nm. Sliding friction tests with single-crystal silicon carbide in contact with iron in a vacuum were characterized by a stock-slip value. The coefficient of friction increased with increasing temperature up to 400 C, then decreased with increasing temperature from 400-600 C. Reheating surfaces to 800 C after preheating them to that temperature produced no changes in AES readings. It is concluded that the maximum density of silicon and silicon-carbide is at 800 C, and the higher the sliding temperature, the more metal that is transferred.

Miyoshi, K.↗