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Material Selection Guidelines to Limit Atomic Oxygen Effects on Spacecraft Surfaces

This report provides guidelines in selecting materials for satellites and space platforms, designed to operate within the Low-Earth orbit environment, which limit the effects of atomic oxygen interactions with spacecraft surfaces. This document should be treated as an introduction rather than a comprehensive guide since analytical and flight technologies continue to evolve, flight experiments are conducted as primary or piggyback opportunities arise, and our understanding of materials interactions and protection methods grows. The reader is urged to consult recent literature and current web sites containing information about research and flight results.

Dooling, D.↗

LEO space environmental effects: TRW LDEF experimental trays

Comprised of two identical trays, the TRW Long Duration Exposure Facility (LDEF) experiment (A0054) provided a unique opportunity to study long term space environmental effects on a variety of materials exposed to two different space environments. The leading edge tray saw micrometeors and anthropogenic space debris, ultraviolet radiation, and energetic atomic oxygen. In contrast, the trailing edge tray was exposed to ultraviolet and micrometeors but saw relatively little, if any, space debris fluence and no energetic atomic oxygen. The striking difference in appearance of the two experimental trays is directly attributable to the nonuniformity of the space environment about the LDEF. It is estimated that the majority of the erosion to the Kapton polyimide dielectric material occurred during the last month on orbit due to the sharply nonlinear increase in atomic oxygen number density as orbital altitude decayed over the life of the mission.

Blakkolb, B. K.↗

Potential energy surfaces for atomic oxygen reactions: Formation of singlet and triplet biradicals as primary reaction products with unsaturated organic molecules

The experimental study of the interaction of atomic oxygen with organic polymer films under LEO conditions has been hampered by the inability to conduct detailed experiments in situ. As a result, studies of the mechanism of oxygen atom reactions have relied on laboratory O-atom sources that do not fully reproduce the orbital environment. For example, it is well established that only ground electronic state O atoms are present at LEO, yet most ground-based sources are known to produce singlet O atoms and molecules and ions in addition to O(3P). Engineers should not rely on such facilities unless it can be demonstrated either that these different O species are inert or that they react in the same fashion as ground state atoms. Ab initio quantum chemical calculations have been aimed at elucidating the biradical intermediates formed during the electrophilic addition of ground and excited-state O atoms to carbon-carbon double bonds in small olefins and aromatic molecules. These biradicals are critical intermediates in any possible insertion, addition and elimination reaction mechanisms. Through these calculations, we will be able to comment on the relative importance of these pathways for O(3P) and O(1D) reactions. The reactions of O atoms with ethylene and benzene are used to illustrate the important features of the mechanisms of atomic oxygen reaction with unsaturated organic compounds and polymeric materials.

Jaffe, Richard L.↗

LADEE UVS Observations of Atoms and Dust in the Lunar Tail

The Lunar Atmosphere and Dust Environment Explorer (LADEE) was a lunar orbiter launched in September 2013 that investigated the composition and temporal variation of the tenuous lunar exosphere and dust environment. A major goal of the mission was to characterize the dust exosphere prior to future lunar exploration activities, which may alter the lunar environment. The Ultraviolet/Visible Spectrometer (UVS) onboard LADEE addresses this goal, utilizing two sets of optics: a limbviewing telescope, and a solar-viewing telescope. We report on spectroscopic (approximately 280 - 820 nm) observations viewing down the lunar wake or along the 'lunar tail' from lunar orbit. Prior groundbased studies have observed the emission from neutral sodium atoms extended along the lunar tail, so often this region is referred to as the lunar sodium tail. UVS measurements were made on the dark side of the moon, with the UVS limb-viewing telescope pointed outward in the direction of the Moon's wake (almost anti-sun), during different lunar phases. These UVS observation activities sample a long column and allow the characterization of scattered light from dust and emission lines from atoms in the lunar tail. Observations in this UVS configuration show the largest excess of scattered blue light in our data set, indicative of the presence of small dust grains in the tail. Once lofted, nanoparticles may become charged and picked up by the solar wind, similar to the phenomena witnessed above Enceladus's northern hemisphere or by the STEREO/WAVES instrument while close to Earth's orbit. The UVS data show that small dust grains as well as atoms become entrained in the lunar tail.

Dust and Solar Wind↗

The measurement of angular differential cross sections at the SSL Atomic Scattering Facility

The design of the SSL Atomic Scattering Facility (ASF) located at the NASA/Marshall Space Flight Center as well as some of the initial experiments to be performed with it, are covered. The goal is to develop an apparatus capable of measuring angular differential cross sections (ADCS) for the scattering of 2 to 14 eV atomic oxygen from various gaseous targets. At present little is known about atomic oxygen scattering with kinetic energies of a few eV. This apparatus is designed to increase the understanding of collisions in this energy region. Atomic oxygen scattering processes are of vital interest to NASA because the space shuttle as well as other low earth orbit satellites will be subjected to a flux of 5 eV atomic oxygen on the ram surfaces while in orbit. The primary experiments will involve the measurements of ADCS for atomic oxygen scattering from gaseous targets (in particular, molecular nitrogen). These, as well as the related initial experiments involving thermal He scattering from N2 and O2 targets will be described.

Kvale, Thomas J.↗

Angularly resolved X-ray photoelectron spectroscopy investigation of PTFE after prolonged space exposure

Monochromatized angularly resolved X-ray photoelectron spectroscopy (ARXPS) was used to study PTFE (Teflon) that had been exposed to an earth orbital environment for approximately six years. The primary interest of the research is on a very reactive component of this environment (atomic oxygen) which, because of the typical orbital velocities of a spacecraft, impinge on exposed surfaces with 5 eV energy. This presentation deals with the method of analysis, the findings as they pertain to a rather complex carbon, oxygen, and fluorine XPS peak analysis, and the character of the valence bands. An improved bias referencing method, based on ARXPS, is also demonstrated for evaluating specimen charging effects. It was found that the polymer molecule tends to resist the atomic oxygen attack by reorienting itself, so that the most electronegative CF3 groups are facing the incoming hyperthermal oxygen atoms. The implications of these findings to ground-based laboratory studies are discussed.

Dalins, I.↗

Atomic Oxygen Environment and Effects Overview

Atomic oxygen is the most predominant constituent in the low Earth orbital environment between the altitudes of 180 and 650 km. It is also a major constituent of the Mars orbital environment. It is very chemically reactive and can oxidize many spacecraft surfaces to form volatile reaction products. The importance of understanding atomic oxygen reactions with materials has led to both flight experiments in low Earth orbit and ground-based testing in vacuum chambers containing atomic oxygen to study its’ effect on materials. Testing has been performed in order to determine the extent of the atomic oxygen reaction and assess material and component durability. In addition, the effectiveness of mitigation techniques such as application of a protective coating, adding fillers, or using shielding and getter materials has also been studied both in flight and ground-based experiments. This presentation will focus on defining atomic oxygen environments, discussing its effect on spacecraft materials, and describing some of the testing and mitigation techniques that have been investigated.

Atomic Oxygen, Low Earth Orbit, Low Mars Orbit, ox↗

Orbiting molecular-beam laboratory

The composition of the atmosphere within the planned orbital envelope of the Space Shuttle and the velocity necessary to maintain a stable orbit within that envelope provide unique conditions for forming a high-purity, moderate energy beam (about 5 eV) of atomic oxygen. At 500 km, for example, atomic oxygen comprises approximately 90% of the atmosphere. Since the mean thermal speed of the ambient atomic oxygen is substantially less than the orbital speed, a high-purity beam can be generated by sweeping through the gas with a series of beam-forming truncated conical shells. Characteristics of the beam, including energy distribution, flux, and purity variation with orbital altitude and methods for lowering the mean energy, are presented. Gas-surface interaction experiments that have been proposed for this laboratory are also discussed.

Outlaw, R. A.↗

Atomic Oxygen Task

This report details work performed by the Center for Applied Optics (CAO) at the University of Alabama in Huntsville (UAH) on the contract entitled 'Atomic Oxygen Task' for NASA's Marshall Space Flight Center (contract NAS8-38609, Delivery Order 109, modification number 1). Atomic oxygen effects on exposed materials remain a critical concern in designing spacecraft to withstand exposure in the Low Earth Orbit (LEO) environment. The basic objective of atomic oxygen research in NASA's Materials & Processes (M&P) Laboratory is to provide the solutions to material problems facing present and future space missions. The objective of this work was to provide the necessary research for the design of specialized experimental test configurations and development of techniques for evaluating in-situ space environmental effects, including the effects of atomic oxygen and electromagnetic radiation on candidate materials. Specific tasks were performed to address materials issues concerning accelerated environmental testing as well as specifically addressing materials issues of particular concern for LDEF analysis and Space Station materials selection.

Hadaway, James B.↗

Plasma/Neutral-Beam Etching Apparatus

Energies of neutral particles controllable. Apparatus developed to produce intense beams of reactant atoms for simulating low-Earth-orbit oxygen erosion, for studying beam-gas collisions, and for etching semiconductor substrates. Neutral beam formed by neutralization and reflection of accelerated plasma on metal plate. Plasma ejected from coaxial plasma gun toward neutralizing plate, where turned into beam of atoms or molecules and aimed at substrate to be etched.

Langer, William↗

Dopant effect of yttrium and the growth and adherence of alumina on nickel-aluminum alloys

The atom superposition and electron delocalization molecular orbital theory and large cluster models have been employed to study cation vacancy diffusion in alpha-Al2O3 and the bonding of alpha-Al2O3 to nickel, aluminum, and yttrium surfaces. Al(3+) diffusion barriers in alpha-Al2O3 by the vacancy mechanism are in reasonable agreement with experiment. The barrier to Y(3+) diffusion is predicted to be much higher. Since addition of yttrium to transition metal alloys is known to reduce the growth rate and stress convolutions in protective alumina scales, this result suggests the rate-limiting step in scale growth is cation vacancy diffusion. This may partially explain the beneficial effect of yttrium dopants on scale adhesion. The theory also predicts a very strong bonding between alumina and yttrium at the surface of the alloy. This may also be important to the adhesion phenomenon. It is also found that aluminum and yttrium atoms bond very strongly to nickel because of charge transfer from their higher lying valence orbitals to the lower lying nickel s-d band.

Anderson, A. B.↗

Adsorption of O2, SO2, and SO3, on nickel oxide - Mechanism for sulfate formation

Calculations based on the atom superposition and electron delocalization molecular orbital technique suggest that O2 will adsorb preferentially end-on at an angle 45 deg from normal on a nickel cation site on the (100) surface of NiO. SO2 adsorption is also stronger on the nickel site; SO2 bonds through the sulfur atom in a plane perpendicular to the surface. Adsorption energies for SO3 on the nickel and oxygen sites are comparable in the preferred orientation in which the SO3 plane is parallel to the surface. The calculations suggest that the strength of adsorption varies as O2 greater than SO2 greater than SO3. On activation, SO3 adsorbed to an O(2-) site forms a trigonal pyramidal SO4 species which yields, with a low barrier, a tetrahedral sulfate anion. Subsequently the anion reorients on the surface. Alternative mechanisms which require the formation of Ni(3+) or O(-) are discussed. NiSO4 thus formed may play a passivating role for the corrosion of Ni at low temperatures in the SO2 + O2 + SO3 atmospheres and an active role at high temperatures, as discussed in the experimental literature.

Mehandru, S. P.↗

Adsorption of O2, SO2, and SO3 on nickel oxide. Mechanism for sulfate formation

Calculations based on the atom superposition and electron delocalization molecular orbital (ASED-MO) technique suggest that O2 will adsorb perferentially end-on at an angle 45 deg from normal on a nickel cation site on the (100) surface of NiO. SO2 adsorption is also stronger on the nickel site; SO2 bonds through the sulfur atom is a plane perpendicular to the surface. Adsorption energies for SO3 on the nickel and oxygen sites are comparable in the perferred orientation in which the SO3 plane is parallel to the surface. On activation, SO3 adsorbed to an O2(-) site forms a trigonal pyramidal SO4 species which yields, with a low barrier, a tetrahedral sulfate anion. Subsequently the anion reorients on the surface. Possibilities for alternative mechanisms which require the formation of Ni3(+) or O2(-) are discussed. NiSO4 thus formed leads to the corrosion of Ni at high temperatures in the SO2+O2/SO3 The SO2+O2/SO3 atmosphere, as discussed in the experimental literature.

Mehandru, S. P.↗

Characterization of polymer films retrieved from LDEF

One of the trays aboard LDEF was an experiment having the objective of assessing the effects of long term exposure of candidate balloon films, tapes, and lines to the hostile environment of space. The fortuitous location of these materials on LDEF minimized direct impact by atomic oxygen thus providing an opportunity to study the effects of low earth orbit environments on polymeric materials without the worry of atomic oxygen abrasion. The resulting chemical, morphological, and thermomechanical changes for polyethylene specimens are reviewed. In addition, preliminary data for fluorinated ethylene/propylene copolymers used for thermal blankets is presented. Polyethylene is observed to crosslink and branch from exposure to atomic oxygen and/or ultraviolet with a decrease in crystallinity.

Letton, Alan↗

Atomic nitrogen in the upper atmosphere of Venus

Atomic nitrogen has been detected in the upper atmosphere of Venus by the Pioneer-Venus Orbiter Neutral Mass Spectrometer (ONMS). Surface recombination of atomic nitrogen with atomic oxygen to form nitric oxide in the ion source allows it to be detected at mass 30. The scale height temperature of the mass 30 peak agrees with the scale height temperatures of the other species if it is assumed to be derived from atomic nitrogen. The diurnal variation of atomic nitrogen is approximately proportional to that of atomic oxygen with an estimated N/O ratio of 1.5% at 150 km.

Kasprzak, W. T.↗

Pulsed Source Of Energetic Oxygen Atoms

Apparatus developed that generates high-flux pulses of oxygen atoms to bombard specimens in experiments on aging and degradation of materials in low Earth-orbit environment. Preliminary studies of specimens irradiated with atomic oxygen provided spectral evidence of erosion, in addition to measurable mass loss. Intense atomic oxygen pulses also useful in studies of microfabrication techniques.

Caledonia, George↗

Advances in atomic oxygen simulation

Atomic oxygen (AO) present in the atmosphere at orbital altitudes of 200 to 700 km has been shown to degrade various exposed materials on Shuttle flights. The relative velocity of the AO with the spacecraft, together with the AO density, combine to yield an environment consisting of a 5 eV beam energy with a flux of 10(exp 14) to 10(exp 15) oxygen atoms/sq cm/s. An AO ion beam apparatus that produces flux levels and energy similar to that encountered by spacecraft in low Earth orbit (LEO) has been in existence since 1987. Test data was obtained from the interaction of the AO ion beam with materials used in space applications (carbon, silver, kapton) and with several special coatings of interest deposited on various surfaces. The ultimate design goal of the AO beam simulation device is to produce neutral AO at sufficient flux levels to replicate on-orbit conditions. A newly acquired mass spectrometer with energy discrimination has allowed 5 eV neutral oxygen atoms to be separated and detected from the background of thermal oxygen atoms of approx 0.2 eV. Neutralization of the AO ion beam at 5 eV was shown at the Martin Marietta AO facility.

Froechtenigt, Joseph F.↗

Oxygen interaction with space-power materials

Data from the space shuttle flights have established that many materials experience relatively rapid degradation when exposed to the low Earth orbit ambient atmosphere, which is predominately atomic oxygen. While much was learned from samples flown on the shuttle, laboratory simulations of the shuttle environment are necessary for a detailed understanding of the various interactions which contribute to the observed degradations. These laboratory experiments are particularly important for predicting the deterioration to be expected for materials aboard orbiting power systems, which will be exposed for long periods of time and could have components operating at very high temperatures. By using a mass spectrometer to synchronously detect molecules emitted from the surface as a result of amplitude modulated oxygen ion bombardment, quantum yields were obtained as a function of ion energy. A technique was developed to obtain preliminary yield data by slowly scanning the mass setting of the mass spectrometer; measurements were extended down to zero modulation frequency; yield data was obtained for the insulating materials (Nomex, Kevlar, and Teflon) used in the construction of electrodynamic tethers; a heated sample holder was constructed to investigate the effect of sample temperature on quantum yields; and the instrumentation was developed to observe the mass spectrometer signal as a function of time during and following bombardment of the sample by a brief (approximately 1 millisecond) pulse of ions.

Eck, T. G.↗