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Trace Oxygen Measurements of Asteroid Sample Storage Desiccators

The Astromaterials Curation facility at the NASA Johnson Space Center is currently curating more than 120 g of carbonaceous asteroid Bennu material as well as over 500 mg of asteroid Ryugu [1 and 2]. These astromaterials are stored in isolating desiccators and gloveboxes under a continuous purge of pure (<1 ppm O 2 ) gaseous nitrogen. The oxygen and moisture concentrations in our OSIRIS-REx sample processing gloveboxes are continuously monitored via integrated sensors; however, our sample storage desiccators lack integrated oxygen and humidity sensors. In previous studies, we used PreSens Fibox 4 trace oxygen meters and optochemical PSt9 spot sensors to measure the oxygen concentrations in candidate asteroid sample containers that had been sealed in nitrogen; we determined that Eagle stainless steel containers inhibit the ingress of external oxygen for several weeks [3]. This optochemical sensor technology allowed us to take precise, contactless measurements within a trace range of 0 to 200 ppmv O 2 . The effectiveness of the trace oxygen sensors in our container experiments inspired us to utilize them to assess the performance of our desiccators that previously lacked trace oxygen monitoring. In this study, our goal was to determine the quality of the nitrogen purge in the isolating desiccator under normal operating conditions by measuring the trace oxygen content. Utilizing optochemical sensor technology, we determined how long the oxygen concentration takes to reach an equilibrium in the desiccator; that is, determine the rate at which the oxygen diffusion into the desiccator equals the rate at which oxygen diffuses out of the desiccator via N2 purge. Additionally, we wanted to determine the oxygen concentration at this equilibrium, the state in which our desiccators are in during normal operating conditions. We tested a custom three chamber desiccator manufactured by Germfree using a PSt9 trace oxygen sensor spot that was mounted into a ¼” National Pipe Tapered (NPT) metal flow-through cell and attached it to the desiccator exhaust. The desiccator consists of top, middle, and bottom isolating chambers. The top chamber door was opened for several minutes to simulate a sample exchange, it was sealed, and then purged ~15 Standard Cubic Feet per Hour (SCFH). Oxygen measurements were automatically recorded via the Fibox 4 trace oxygen meter in 5-minute intervals over the course of a 24-hour period. Our results indicate the desiccator reached an equilibrium value of 10-15 ppm O 2 after ~5 hours (Fig. 1). This data allows us to explore standards for purging and exchange protocols that can be applied to similar types of desiccators in Hayabusa2, OSIRIS-REx, and for sample return collections. The assessment of the internal gaseous compositions of desiccators also allows us to share with the community the N 2 environment in which many of our asteroid samples and hardware are securely curated. Future measurements will include other nitrogen flow rates and measuring the trace oxygen concentration as a function of time for the levels of the previous commercial desiccator in which the Hayabusa2 sample collection was stored. We will also analyze how long the desiccators hold N2 after being disconnected from their N2 source, an extended measurement for sample security reassurance.

Curation↗

Cleaning Carbon Nanotubes by Use of Mild Oxygen Plasmas

Experiments have shown that it is feasible to use oxygen radicals (specifically, monatomic oxygen) from mild oxygen plasmas to remove organic contaminants and chemical fabrication residues from the surfaces of carbon nanotubes (CNTs) and metal/CNT interfaces. A capability for such cleaning is essential to the manufacture of reproducible CNT-based electronic devices. The use of oxygen radicals to clean surfaces of other materials is fairly well established. However, previously, cleaning of CNTs and of graphite by use of oxygen plasmas had not been attempted because both of these forms of carbon were known to be vulnerable to destruction by oxygen plasmas. The key to success of the present technique is, apparently, to ensure that the plasma is mild . that is to say, that the kinetic and internal energies of the oxygen radicals in the plasma are as low as possible. The plasma oxygen-radical source used in the experiments was a commercial one marketed for use in removing hydrocarbons and other organic contaminants from vacuum systems and from electron microscopes and other objects placed inside vacuum systems. In use, the source is installed in a vacuum system and air is leaked into the system at such a rate as to maintain a background pressure of .0.56 torr (.75 Pa). In the source, oxygen from the air is decomposed into monatomic oxygen by radio-frequency excitation of a resonance of the O2 molecule (N2 is not affected). Hence, what is produced is a mild (non-energetic) oxygen plasma. The oxygen radicals are transported along with the air molecules in the flow created by the vacuum pump. In the experiments, exposure to the oxygen plasma in this system was shown to remove organic contaminants and chemical fabrication residues from several specimens. Many high-magnification scanning electron microscope (SEM) images of CNTs were taken before and after exposure to the oxygen plasma. As in the example shown in the figure, none of these images showed evidence of degradation of CNT structures.

Petkov, Mihail↗

A Cabin Air Separator for EVA Oxygen

Presently, the Extra-Vehicular Activities (EVAs) conducted from the Quest Joint Airlock on the International Space Station use high pressure, high purity oxygen that is delivered to the Space Station by the Space Shuttle. When the Space Shuttle retires, a new method of delivering high pressure, high purity oxygen to the High Pressure Gas Tanks (HPGTs) is needed. One method is to use a cabin air separator to sweep oxygen from the cabin air, generate a low pressure/high purity oxygen stream, and compress the oxygen with a multistage mechanical compressor. A main advantage to this type of system is that the existing low pressure oxygen supply infrastructure can be used as the source of cabin oxygen. ISS has two water electrolysis systems that deliver low pressure oxygen to the cabin, as well as chlorate candles and compressed gas tanks on cargo vehicles. Each of these systems can feed low pressure oxygen into the cabin, and any low pressure oxygen source can be used as an on-board source of oxygen. Three different oxygen separator systems were evaluated, and a two stage Pressure Swing Adsorption system was selected for reasons of technical maturity. Two different compressor designs were subjected to long term testing, and the compressor with better life performance and more favorable oxygen safety characteristics was selected. These technologies have been used as the basis of a design for a flight system located in Equipment Lock, and taken to Preliminary Design Review level of maturity. This paper describes the Cabin Air Separator for EVA Oxygen (CASEO) concept, describes the separator and compressor technology trades, highlights key technology risks, and describes the flight hardware concept as presented at Preliminary Design Review (PDR)

Graf, John C.↗

Module for Oxygenating Water without Generating Bubbles

A module that dissolves oxygen in water at concentrations approaching saturation, without generating bubbles of oxygen gas, has been developed as a prototype of improved oxygenators for water-disinfection and water-purification systems that utilize photocatalyzed redox reactions. Depending on the specific nature of a water-treatment system, it is desirable to prevent the formation of bubbles for one or more reasons: (1) Bubbles can remove some organic contaminants from the liquid phase to the gas phase, thereby introducing a gas-treatment problem that complicates the overall water-treatment problem; and/or (2) in some systems (e.g., those that must function in microgravity or in any orientation in normal Earth gravity), bubbles can interfere with the flow of the liquid phase. The present oxygenation module (see Figure 1) is a modified version of a commercial module that contains >100 hollow polypropylene fibers with a nominal pore size of 0.05 m and a total surface area of 0.5 m2. The module was originally designed for oxygenation in a bioreactor, with no water flowing around or inside the tubes. The modification, made to enable the use of the module to oxygenate flowing water, consisted mainly in the encapsulation of the fibers in a tube of Tygon polyvinyl chloride (PVC) with an inside diameter of 1 in. (approx.=25 mm). In operation, water is pumped along the insides of the hollow fibers and oxygen gas is supplied to the space outside the hollow tubes inside the PVC tube. In tests, the pressure drops of water and oxygen in the module were found to be close to zero at water-flow rates ranging up to 320 mL/min and oxygen-flow rates up to 27 mL/min. Under all test conditions, no bubbles were observed at the water outlet. In some tests, flow rates were chosen to obtain dissolved-oxygen concentrations between 25 and 31 parts per million (ppm) . approaching the saturation level of approx.=35 ppm at a temperature of 20 C and pressure of 1 atm (approx.=0.1 MPa). As one would expect, it was observed that the time needed to bring a flow of water from an initial low dissolved-oxygen concentration (e.g., 5 ppm) to a steady high dissolved-oxygen concentration at or near the saturation level depends on the rates of flow of both oxygen and water, among other things. Figure 2 shows the results of an experiment in which a greater flow of oxygen was used during the first few tens of minutes to bring the concentration up to approx.=25 ppm, then a lesser flow was used to maintain the concentration.

Gonzalez-Martin, Anuncia↗

Method of Separating Oxygen From Spacecraft Cabin Air to Enable Extravehicular Activities

Extravehicular activities (EVAs) require high-pressure, high-purity oxygen. Shuttle EVAs use oxygen that is stored and transported as a cryogenic fluid. EVAs on the International Space Station (ISS) presently use the Shuttle cryo O2, which is transported to the ISS using a transfer hose. The fluid is compressed to elevated pressures and stored as a high-pressure gas. With the retirement of the shuttle, NASA has been searching for ways to deliver oxygen to fill the highpressure oxygen tanks on the ISS. A method was developed using low-pressure oxygen generated onboard the ISS and released into ISS cabin air, filtering the oxygen from ISS cabin air using a pressure swing absorber to generate a low-pressure (high-purity) oxygen stream, compressing the oxygen with a mechanical compressor, and transferring the high-pressure, high-purity oxygen to ISS storage tanks. The pressure swing absorber (PSA) can be either a two-stage device, or a single-stage device, depending on the type of sorbent used. The key is to produce a stream with oxygen purity greater than 99.5 percent. The separator can be a PSA device, or a VPSA device (that uses both vacuum and pressure for the gas separation). The compressor is a multi-stage mechanical compressor. If the gas flow rates are on the order of 5 to 10 lb (.2.3 to 4.6 kg) per day, the compressor can be relatively small [3 ~16 ~16 in. (.8 ~41 ~41 cm)]. Any spacecraft system, or other remote location that has a supply of lowpressure oxygen, a method of separating oxygen from cabin air, and a method of compressing the enriched oxygen stream, has the possibility of having a regenerable supply of highpressure, high-purity oxygen that is compact, simple, and safe. If cabin air is modified so there is very little argon, the separator can be smaller, simpler, and use less power.

Graf, John C.↗

Measurement and Control of Oxygen Partial Pressure in an Electrostatic Levitator

Recently the NASA Marshall Space Flight Center electrostatic levitation (ESL) laboratory has been upgraded to include an oxygen control system. This system allows the oxygen partial pressure within the vacuum chamber to be measured and controlled, at elevated temperatures, theoretically in the range from 10(exp -36) to 10(exp 0) bar. The role of active surface agents in liquid metals is fairly well known; however, published surface tension data typically has large scatter, which has been hypothesized to be caused by the presence of oxygen. The surface tension of metals is affected by even a small amount of adsorption of oxygen. It has even been shown that oxygen partial pressures may need to be as low as 10(exp -24) bar to avoid oxidation. While electrostatic levitation is done under high vacuum, oxide films or dissolved oxygen may have significant effects on materials properties, such as surface tension and viscosity. Therefore, the ability to measure and control the oxygen partial pressure within the chamber is highly desirable. The oxygen control system installed at MSFC contains a potentiometric sensor, which measures the oxygen partial pressure, and an oxygen ion pump. In the pump, a pulse-width modulated electric current is applied to yttrium-stabilized zirconia, resulting in oxygen transfer into or out of the system. Also part of the system is a control unit, which consists of temperature controllers for the sensor and pump, PID-based current loop for the ion pump, and a control algorithm. This system can be used to study the effects of oxygen on the thermophysical properties of metals, ceramics, glasses, and alloys. It can also be used to provide more accurate measurements by processing the samples at very low oxygen partial pressures. The oxygen control system will be explained in more detail and an overview of its use and limitations in an electrostatic levitator will be described. Some preliminary measurements have been made, and the results to date will be provided.

SanSoucie, Michael P.↗

Monte Carlo Computational Modeling of Atomic Oxygen Interactions

Computational modeling of the erosion of polymers caused by atomic oxygen in low Earth orbit (LEO) is useful for determining areas of concern for spacecraft environment durability. Successful modeling requires that the characteristics of the environment such as atomic oxygen energy distribution, flux, and angular distribution be properly represented in the model. Thus whether the atomic oxygen is arriving normal to or inclined to a surface and whether it arrives in a consistent direction or is sweeping across the surface such as in the case of polymeric solar array blankets is important to determine durability. When atomic oxygen impacts a polymer surface it can react removing a certain volume per incident atom (called the erosion yield), recombine, or be ejected as an active oxygen atom to potentially either react with other polymer atoms or exit into space. Scattered atoms can also have a lower energy as a result of partial or total thermal accommodation. Many solutions to polymer durability in LEO involve protective thin films of metal oxides such as SiO2 to prevent atomic oxygen erosion. Such protective films also have their own interaction characteristics. A Monte Carlo computational model has been developed which takes into account the various types of atomic oxygen arrival and how it reacts with a representative polymer (polyimide Kapton H) and how it reacts at defect sites in an oxide protective coating, such as SiO2 on that polymer. Although this model was initially intended to determine atomic oxygen erosion behavior at defect sites for the International Space Station solar arrays, it has been used to predict atomic oxygen erosion or oxidation behavior on many other spacecraft components including erosion of polymeric joints, durability of solar array blanket box covers, and scattering of atomic oxygen into telescopes and microwave cavities where oxidation of critical component surfaces can take place. The computational model is a two dimensional model which has the capability to tune the interactions of how the atomic oxygen reacts, scatters, or recombines on polymer or nonreactive surfaces. In addition to the specification of atomic oxygen arrival details, a total of 15 atomic oxygen interaction parameters have been identified as necessary to properly simulate observed interactions and resulting polymer erosion that have been observed in LEO. The tuning of the Monte Carlo model has been accomplished by adjusting interaction parameters so the erosion patterns produced by the model match those from several actual LEO space experiments. Surface texturing in LEO can also be predicted by the model. Such comparison of space tests with ground laboratory experiments have enabled confidence in ground laboratory lifetime prediction of protected polymers. Results of Monte Carlo tuning, examples of surface texturing and undercutting erosion prediction, and several examples of how the model can be used to predict other LEO and Mars orbital space results are presented.

Monte Carlo Modeling↗

Monte Carlo Computational Modeling of Atomic Oxygen Interactions

Computational modeling of the erosion of polymers caused by atomic oxygen in low Earth orbit (LEO) is useful for determining areas of concern for spacecraft environment durability. Successful modeling requires that the characteristics of the environment such as atomic oxygen energy distribution, flux, and angular distribution be properly represented in the model. Thus whether the atomic oxygen is arriving normal to or inclined to a surface and whether it arrives in a consistent direction or is sweeping across the surface such as in the case of polymeric solar array blankets is important to determine durability. When atomic oxygen impacts a polymer surface it can react removing a certain volume per incident atom (called the erosion yield), recombine, or be ejected as an active oxygen atom to potentially either react with other polymer atoms or exit into space. Scattered atoms can also have a lower energy as a result of partial or total thermal accommodation. Many solutions to polymer durability in LEO involve protective thin films of metal oxides such as SiO2 to prevent atomic oxygen erosion. Such protective films also have their own interaction characteristics. A Monte Carlo computational model has been developed which takes into account the various types of atomic oxygen arrival and how it reacts with a representative polymer (polyimide Kapton H) and how it reacts at defect sites in an oxide protective coating, such as SiO2 on that polymer. Although this model was initially intended to determine atomic oxygen erosion behavior at defect sites for the International Space Station solar arrays, it has been used to predict atomic oxygen erosion or oxidation behavior on many other spacecraft components including erosion of polymeric joints, durability of solar array blanket box covers, and scattering of atomic oxygen into telescopes and microwave cavities where oxidation of critical component surfaces can take place. The computational model is a two dimensional model which has the capability to tune the interactions of how the atomic oxygen reacts, scatters, or recombines on polymer or nonreactive surfaces. In addition to the specification of atomic oxygen arrival details, a total of 15 atomic oxygen interaction parameters have been identified as necessary to properly simulate observed interactions and resulting polymer erosion that have been observed in LEO. The tuning of the Monte Carlo model has been accomplished by adjusting interaction parameters so the erosion patterns produced by the model match those from several actual LEO space experiments. Surface texturing in LEO can also be predicted by the model. Such comparison of space tests with ground laboratory experiments have enabled confidence in ground laboratory lifetime prediction of protected polymers. Results of Monte Carlo tuning, examples of surface texturing and undercutting erosion prediction, and several examples of how the model can be used to predict other LEO and Mars orbital space results are presented.

Atomic Oxygen↗

Effects of oxygen on the tensile properties and fracture behavior of the Ta-10 W refractory alloy at quasi-static and impact strain rates

This study investigates effects of pre-charged oxygen at levels up to ∼1750 ppm on the tensile properties of the refractory alloy Ta-10 W. Tests were conducted at temperatures to 1100 °C and strain rates from quasi-static (∼10−3 s−1) to impact (∼103 s−1). At all temperatures, ductility decreased with increasing oxygen concentration and could be visually identified as a ductile-to-brittle transition (DBT). Additionally, for a given oxygen concentration, ductility was lower at impact strain rate than at quasi-static. The DBT was accompanied by a change from ductile transgranular to more brittle modes, intergranular and transgranular cleavage. The oxygen concentrations associated with the DBT depend on test temperature and strain rate. However, the transitions themselves are not sharp and cannot be defined as occurring at a specific oxygen concentration. At impact strain rates, ductility is relatively insensitive to test temperatures in the range 300–1100 °C with similar embrittling effects of oxygen; however, oxygen has a more severe embrittling effect at room temperature. This behavior is reversed at quasi-static strain rates where the embrittling effect of oxygen is more severe at elevated temperatures than at room temperature. It appears this difference is related to the kinetics of oxygen diffusion to grain boundaries and crack tips. Specimens that were not pre-charged with oxygen but tensile tested in various partial pressures of oxygen underwent dynamic embrittlement during the test, with the degree of embrittlement increasing as the partial pressure of oxygen in the environment increased. Consistent with such a mechanism, ductility increased with increasing strain rate for a given oxygen partial pressure, which would be the reverse if only intrinsic dislocation mobilities were controlling.

Miller, Roger [ORNL] (ORCID:0000000172155851)↗

Materials International Space Station Experiment-6 (MISSE-6) Atomic Oxygen Fluence Monitor Experiment

An atomic oxygen fluence monitor was flown as part of the Materials International Space Station Experiment-6 (MISSE-6). The monitor was designed to measure the accumulation of atomic oxygen fluence with time as it impinged upon the ram surface of the MISSE 6B Passive Experiment Container (PEC). This was an active experiment for which data was to be stored on a battery-powered data logger for post-flight retrieval and analysis. The atomic oxygen fluence measurement was accomplished by allowing atomic oxygen to erode two opposing wedges of pyrolytic graphite that partially covered a photodiode. As the wedges of pyrolytic graphite erode, the area of the photodiode that is illuminated by the Sun increases. The short circuit current, which is proportional to the area of illumination, was to be measured and recorded as a function of time. The short circuit current from a different photodiode, which was oriented in the same direction and had an unobstructed view of the Sun, was also to be recorded as a reference current. The ratio of the two separate recorded currents should bear a linear relationship with the accumulated atomic oxygen fluence and be independent of the intensity of solar illumination. Ground hyperthermal atomic oxygen exposure facilities were used to evaluate the linearity of the ratio of short circuit current to the atomic oxygen fluence. In flight, the current measurement circuitry failed to operate properly, thus the overall atomic oxygen mission fluence could only be estimated based on the physical erosion of the pyrolytic graphite wedges. The atomic oxygen fluence was calculated based on the knowledge of the space atomic oxygen erosion yield of pyrolytic graphite measured from samples on the MISSE 2. The atomic oxygen fluence monitor, the expected result and comparison of mission atomic oxygen fluence based on the erosion of the pyrolytic graphite and Kapton H atomic oxygen fluence witness samples are presented in this paper.

Banks, Bruce A.↗

Atomic Oxygen Fluence Monitor

This innovation enables a means for actively measuring atomic oxygen fluence (accumulated atoms of atomic oxygen per area) that has impinged upon spacecraft surfaces. Telemetered data from the device provides spacecraft designers, researchers, and mission managers with real-time measurement of atomic oxygen fluence, which is useful for prediction of the durability of spacecraft materials and components. The innovation is a compact fluence measuring device that allows in-space measurement and transmittance of measured atomic oxygen fluence as a function of time based on atomic oxygen erosion yields (the erosion yield of a material is the volume of material that is oxidized per incident oxygen atom) of materials that have been measured in low Earth orbit. It has a linear electrical response to atomic oxygen fluence, and is capable of measuring high atomic oxygen fluences (up to >10(exp 22) atoms/sq cm), which are representative of multi-year low-Earth orbital missions (such as the International Space Station). The durability or remaining structural lifetime of solar arrays that consist of polymer blankets on which the solar cells are attached can be predicted if one knows the atomic oxygen fluence that the solar array blanket has been exposed to. In addition, numerous organizations that launch space experiments into low-Earth orbit want to know the accumulated atomic oxygen fluence that their materials or components have been exposed to. The device is based on the erosion yield of pyrolytic graphite. It uses two 12deg inclined wedges of graphite that are over a grit-blasted fused silica window covering a photodiode. As the wedges erode, a greater area of solar illumination reaches the photodiode. A reference photodiode is also used that receives unobstructed solar illumination and is oriented in the same direction as the pyrolytic graphite covered photodiode. The short-circuit current from the photodiodes is measured and either sent to an onboard data logger, or transmitted to a receiving station on Earth. By comparison of the short-circuit currents from the fluence-measuring photodiode and the reference photodiode, one can compute the accumulated atomic oxygen fluence arriving in the direction that the fluence monitor is pointing. The device produces a signal that is linear with atomic oxygen fluence using a material whose atomic oxygen erosion yield has been measured over a period of several years in low-Earth orbit.

Banks, Bruce A.↗

Methanol Partial Oxidation on Cu(111) and PtCu(111) Single-Atom Alloy Surfaces: Effect of Surface Oxygen Coverage on Selectivity

The selective oxidation of methanol to formaldehyde on Cu surfaces is an important and well-studied reaction. However, a systematic analysis of product selectivity as a function of oxygen coverage on Cu(111) and Cu-based single-atom alloys (SAAs) has not been previously reported. In this work, we present a comprehensive investigation of deuterated methanol (CD 3 OH) partial oxidation on Cu(111) and 1% PtCu(111) SAA surfaces as a function of preadsorbed oxygen coverage. Temperature-programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS) reveal that isolated Pt atoms inhibit the initial surface oxidation of Cu(111) under low oxygen exposures. Despite this difference in oxidation kinetics, the product selectivity remains largely unaffected: on both Cu(111) and PtCu(111), formaldehyde (CD 2 O) is the predominant partial oxidation product over a broad range of oxygen coverages. The selectivity toward formaldehyde peaks at intermediate oxygen coverages (∼0.3 monolayers, ML), indicating the existence of an optimal oxygen loading for partial oxidation. Notably, the similar product selectivities on Cu(111) and PtCu(111) over a range of surface oxygen coverage indicate that Pt single atoms do not significantly alter the reaction pathway or shift the optimal oxygen coverage for formaldehyde formation. Control experiments confirm that Cu(111) is unreactive toward methanol in the absence of oxygen, while PtCu(111) surfaces produce a small amount of formaldehyde even when oxygen is not preadsorbed, indicating that isolated Pt atoms facilitate O−H activation at below 150 K, leading to H 2 desorption, followed by C−D activation at higher temperatures (∼350 K). Density functional theory (DFT)-based calculations show that Pt atoms increase the O 2 dissociation barrier relative to Cu(111), consistent with the observed inhibition of oxidation at low exposures. Overall, this work provides the first detailed selectivity map for methanol oxidation on oxidized Cu(111) and PtCu(111) SAA surfaces. By linking classical mechanistic insights such as methoxy- and formate-mediated pathways with single-atom alloy catalyst design, this work demonstrates that while Pt substitution modulates the oxidation kinetics and oxygen binding, the overall selectivity toward formaldehyde is governed primarily by oxygen coverage. These findings underscore the potential of isolated dopants to tune surface oxidation behavior without compromising the intrinsic partial oxidation selectivity of copper-based catalysts.

36 MATERIALS SCIENCE↗

Effect of oxygen and nitrogen interactions on friction of single-crystal silicon carbide

Friction studies were conducted with single-crystal silicon carbide contacting silicon carbide and titanium after having been exposed to oxygen and nitrogen in various forms. After they had been sputter cleaned, the surfaces were (1) exposed to gaseous oxygen and nitrogen (adsorption), (2) ion bombarded with oxygen and nitrogen, or (3) reacted with oxygen (SiC only). Auger emission spectroscopy was used to determine the presence of oxygen and nitrogen. The results indicate that the surfaces of silicon carbide with reacted and ion-bombarded oxygen ions give higher coefficients of friction than do argon sputter-cleaned surfaces. The effects of oxygen on friction may be related to the relative chemical, thermodynamic properties of silicon, carbon, and titanium for oxygen. The adsorbed films of oxygen, nitrogen, and mixed gases of oxygen and nitrogen on sputter-cleaned, oxygen-ion bombarded, and oxygen-reacted surfaces generally reduce friction. Adsorption to silicon carbide is relatively weak.

Miyoshi, K.↗

Electrochemical cell for obtaining oxygen from carbon dioxide atmospheres

For manned missions to Mars to become a reality, an efficient and reliable means of obtaining oxygen from the carbon dioxide-rich atmosphere will be required. Otherwise, the high cost of transporting the oxygen needed to sustain the astronauts will severely restrict the expedition to the martian surface. Recently, the use of electrochemical devices has been explored as a means of obtaining oxygen from the carbon dioxide-rich atmosphere. In these devices, oxygen ions diffuse through solid oxide membranes, thus, separating oxygen from the other gases presented. This phenomenon has only recently been explored as a means of obtaining large quantities of oxygen from toxic atmospheres, although first observed by Walter nernst in 1899. Nernst observed that stabilized zirconia will conduct oxygen ions when an electrical potential is applied across metallic electrodes applied to the ceramic membrane. Diatomic oxygen molecules are dissociated at the positive electrode/electrolyte interface. The oxygen ions enter the ceramic body due to the ion density gradient which is produced by the electrical potential across the electrolytic membrane. Once the ions have diffused through the membrane, they reform diatomic oxygen molecules at the anode. The separation of oxygen from carbon dioxide is achieved by the combination of thermal and electrochemical processes. The thermal decomposition of carbon dioxide (at 1000 C) results in the production of carbon monoxide and oxygen by the reaction.

Hooker, M. W.↗

Atomic oxygen interaction at defect sights in protective coatings on polymers flown on LDEF

Although the Long Duration Exposure Facility (LDEF) has exposed materials with a fixed orientation relative to the ambient low-Earth-orbital environment, arrival of atomic oxygen is angularly distributed as a result of the atomic oxygen's high temperature Maxwellian velocity distribution and the LDEF's orbital inclination. Thus, atomic oxygen entering defects in protective coatings on polymeric surfaces can cause wider undercut cavities than the size of the defect in the protective coating. Because only a small fraction of atomic oxygen reacts upon first impact with most polymeric materials, secondary reactions with lower energy thermally accommodated atomic oxygen can occur. The secondary reactions of scattered and/or thermally accommodated atomic oxygen also contribute to widening the undercut cavity beneath the protective coating defect. As the undercut cavity enlarges, exposing more polymer, the probability of atomic oxygen reacting with underlying polymeric material increases because of multiple opportunities for reaction. Thus, the effective atomic oxygen erosion yield for atoms entering defects increases above that of the unprotected material. Based on the results of analytical modeling and computational modeling, aluminized Kapton multilayer insulation exposed to atomic oxygen on row 9 lost the entire externally exposed layer of polyimide Kapton, yet based on the results of this investigation, the bottom surface aluminum film must have remained in place, but crazed. Atomic oxygen undercutting at defect sites in protective coatings on graphite epoxy composites indicates that between 40 to 100 percent of the atomic oxygen thermally accommodates upon impact, and that the reaction probability of thermally accommodated atomic oxygen may range from 7.7 x 10(exp -6) to 2.1 x 10(exp -3), depending upon the degree of thermal accommodation upon each impact.

Banks, Bruce A.↗

Reaction and Protection of Electrical Wire Insulators in Atomic-oxygen Environments

Atomic-oxygen erosion on spacecraft in low Earth orbit is an issue which is becoming increasingly important because of the growing number of spacecraft that will fly in the orbits which have high concentrations of atomic oxygen. In this investigation, the atomic-oxygen durability of three types of electrical wire insulation (carbon-based, fluoropolymer, and polysiloxane elastomer) were evaluated. These insulation materials were exposed to thermal-energy atomic oxygen, which was obtained by RF excitation of air at a pressure of 11-20 Pa. The effects of atomic-oxygen exposure on insulation materials indicate that all carbon-based materials erode at about the same rate as polyamide Kapton and, therefore, are not atomic-oxygen durable. However, the durability of fluoropolymers needs to be evaluated on a case by case basis because the erosion rates of fluoropolymers vary widely. For example, experimental data suggest the formation of atomic fluorine during atomic-oxygen amorphous-fluorocarbon reactions. Dimethyl polysiloxanes (silicone) do not lose mass during atomic-oxygen exposure, but develop silica surfaces which are under tension and frequently crack as a result of loss of methyl groups. However, if the silicone sample surfaces were properly pretreated to provide a certain roughness, atomic oxygen exposure resulted in a sturdy, non-cracked atomic-oxygen durable SiO2 layer. Since the surface does not crack during such silicone-atomic oxygen reaction, the crack-induced contamination by silicone can be reduced or completely stopped. Therefore, with proper pretreatment, silicone can be either a wire insulation material or a coating on wire insulation materials to provide atomic-oxygen durability.

Hung, Ching-Cheh↗

Oxygen Systems Cleaners for Aerospace Applications

New environmental regulations have forced extensive evaluations of many different cleaning agents for use in oxygen systems. This is no simple process because pure oxygen is a very strong oxidizer, and when placed in contact with a foreign substance, the combination may be explosive. This foreign substance can easily be a cleaning agent residue left over in the oxygen system after cleaning. This paper focuses on the factors that must be considered when selecting a cleaning agent for oxygen systems, as well as the approval processes which are currently being utilized by NASA for oxygen compatibility of materials. This paper will provide a working description of how to begin selecting a cleaning agent for oxygen systems. The paper will present the following: Background information on the necessity of a stringent selection process for oxygen system cleaners; Specifications and regulations concerning cleaning for oxygen service; Changing oxygen cleaning specifications given current environmental concerns; Testing for cleanliness in oxygen systems, Cleaning agents that have been tested for oxygen systems, including an extensive list of some of the newer 'environmentally friendly' cleaning agents; and Test results and conclusions from the testing. The paper will also provide instructions on the proper procedures for obtaining NASA approval on a candidate oxygen systems cleaning agent.

Davis, Samuel E.↗

Photochemistry Saturn's Atmosphere: Effects of an Influx of External Oxygen - 2

We use a one-dimensional diurnally averaged model of photochemistry and diffusion in Saturn's stratosphere to investigate the influence of extraplanetary debris on atmospheric chemistry. In particular, we consider the effects of an influx of oxygen from micrometeoroid ablation or from ring-particle diffusion; the contribution from cometary impacts, satellite debris, or ring vapor is deemed to be less important. The photochemical model results are compared directly with Infrared Space Observatory (ISO) observations to constrain the influx of extraplanetary oxygen to Saturn. From the ISO observations, we determine that the column densities of CO2 and H2O above 10 mbar in Saturn's atmosphere are (6.3 +/- 1) x 10(exp 14) and (1.4 +/- 0.4) x 10(exp 15)/ square cm, respectively; our models indicate that a globally averaged oxygen influx of (4+/-2) x 10(exp 6) O atoms /sq cm/s is required to explain these observations. Models with a locally enhanced influx of H20 operating over a small fraction of the projected area do not provide as good a fit to the ISO H2O observations. If volatile oxygen compounds comprise one-third to one-half of the exogenic source by mass, then Saturn is currently being bombarded with (3 +/- 2) x 10(exp -16) g/square cm/s of extraplanetary material. To reproduce the observed CO2/H2O ratio in Saturn's stratosphere, some of the exogenic oxygen must arrive in the form of a carbon-oxygen bonded species such as CO or CO2. An influx consistent with the composition of cometary ices fails to reproduce the high observed CO2/H2O ratio, suggesting that (i) the material has ices that are slightly more carbon-rich than is typical for comets, (ii) a contribution from an organic-rich component is required, or (iii) some of the hydrogen-oxygen bonded material is converted to carbon-oxygen bonded material without photochemistry (e.g., during the ablation process). We have also reanalyzed the 5-micron CO observations of Noll and Larson and determine that the CO lines are most sensitive to the 100- to 400-mbar column density for which we derive a range of (0.7-1.5) x 10(exp 17)/square cm; the CO observations do not allow us to distinguish between an external or internal source of CO on Saturn. If we assume that all the extraplanetary oxygen derives from a micrometeoroid source, then the unfocused dust flux at 9.5 AU must be (i) (1 +/- 0.7) x 10(exp -16) g/square cm/s if interstellar grains are the source of the external oxygen on Saturn, (ii) (4 +/- 3) x 10 (exp -17) g/ sq. cm./s if IDPs on randomly inclined, highly eccentric orbits (e.g., Halley-type comet grains) are the source of the external oxygen, or (iii) (2+/- 1.4) x 10(exp -18)/g/sq cm/s if IDPs on low inclination, low eccentricity orbits (e.g., Kuiper-belt grains) are the source of the external oxygen. These estimates can be used in combination with future Cassini dust detection data to determine the ultimate source of the dust at Saturn's distance from the Sun.

Moses, Julianne I.↗