Correlation of oxygen concentration and activated oxygen donors in silicon crystals on a microscale
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Rava, P.↗
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Electron Spin Resonance (ESR) detection of active oxygen species and organic phases in Martian soils
The presence of active oxygen species (O(-), O2(-), O3(-)) and other strong oxidants (Fe2O3 and Fe3O4) was invoked in interpretations of the Viking biological experiments and a model was also suggested for Martian surface chemistry. The non-biological interpretations of the biological results gain futher support as no organic compounds were detected in the Viking pyrolysis-gas chromatography mass spectrometer (GCSM) experiments at concentrations as low as 10 ppb. Electron spin resonance (ESR) measures the absorption of microwaves by a paramagnetic and/or ferromagnetic center in the presence of an external field. In many instances, ESR has the advantage of detailed submicroscopic identification of the transient species and/or unstable reaction intermediates in their environments. Since the higly active oxygen species (O(-), O2(-), O3(-), and R-O-O(-)) are all paramagnetic in nature, they can be readily detected in native form by the ESR method. Active oxygen species likely to occur in the Martian surface samples were detected by ESR in UV-irradiated samples containing MgO. A miniaturized ESR spectrometer system can be developed for the Mars Rover Sample Return Mission. The instrument can perform the following in situ Martian samples analyses: detection of active oxygen species; characterization of Martian surface chemistry and photooxidation processes; and searching for organic compounds in the form of free radicals preserved in subsoils, and detection of microfossils with Martian carbonate sediments.
Tsay, Fun-Dow↗
Enhanced oxidation of platinum in activated oxygen. III - Kinetics and mechanism.
Kinetics and mechanism of enhanced oxidation of platinum in activated oxygen as function of partial pressure of oxygen atoms
ACTIVATION ENERGY↗
Activated oxygen ashing of biological specimens for the microdetermination of Na, K, Mg, and Ca by atomic absorption spectrophotometry.
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Sanui, H.↗
Assembly of Modified Ferritin Proteins on Carbon Nanotubes and its Electrocatalytic Activity for Oxygen Reduction
Highly effective dispersions of carbon nanotubes (CNTs) can be made using a commercially available buffer solution. Buffer solutions of 3-(N-morpholino)-propanesulfonic acid (MOPS), which consists of a cyclic ring with nitrogen and oxygen heteroatoms, a charged group, and an alkyl chain greatly enhance the dispersibility and stability of CNTs in aqueous solutions. Additionally, the ability of biomolecules, especially cationized Pt-cored ferritins, to adhere onto the well-dispersed CNTs in the aqueous buffer solution is also improved. This was accomplished without the use of surfactant molecules, which are detrimental to the electrical, mechanical, and other physical properties of the resulting products. The assembled Pt-cored ferritin proteins on the CNTs were used as an electrocatalyst for oxygen reduction
Kim, Jae-Woo↗
Highly Active Bifunctional Oxygen Electrocatalytic Sites Realized in Ceria–Functionalized Graphene
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Simranjit Grewal↗
Chemical interpretation of Viking Lander 1 life detection experiment
An earth-based evaluation of the Viking Lander 1 life-detection experiments was conducted using a radiofrequency glow discharge in a simulated Martian atmosphere. The Gas Exchange Experiment conducted in the humid mode released substantial amounts of CO2, O2, N2, Ar, and CO into the atmosphere, indicating that these substances were adsorbed onto the Martian soil. An adsorption potential plot is given, graphing quantity of gas against time (d). For a model surface area of 17 squares meters per gram of measured substance, oxygen adsorption was found to be relatively high, a result which tends to confirm the hypothesis that Martian oxygen exists largely in chemisorbed states or in active oxygen compounds, e.g., peroxide, superoxide, hydroperoxide
Ballou, E. V.↗
Report on ISS Oxygen Production, Resupply, and Partial Pressure Management
The majority of oxygen used on International Space Station (ISS) is for metabolic support and denitrogenation procedures prior to Extra-Vehicular Activities. Oxygen is supplied by various visiting vehicles such as the Progress and Shuttle in addition to oxygen production capability on both the United States On-Orbit Segment (USOS) and Russian Segment (RS). To maintain a habitable atmosphere the oxygen partial pressure is controlled between upper and lower bounds. The full range of the allowable oxygen partial pressure along with the increased ISS cabin volume is utilized as a buffer allowing days to pass between oxygen production or direct addition of oxygen to the atmosphere from reserves. This paper summarizes amount of oxygen supplied and produced from all of the sources and describes past experience of managing oxygen partial pressure along with the range of management options available to the ISS.
Schaezler, Ryan↗
High-surface-area, dual-function oxygen electrocatalysts for space power applications
The processes of hydration/dehydration and carbonation/decarbonation are investigated as an approach to provide higher surface area mixed metal oxides that are more active electrochemically. These materials are candidates for use as electrocatalysts and electrocatalyst supports for alkaline electrolyzers and fuel cells. For the case of the perovskite, LaCoO3 , higher surface areas were achieved with no change in structure and a more active oxygen electrocatalyst.
Ham, David O.↗
Oxidation of SiC/BN/SiC Composites in Reduced Oxygen Partial Pressures
SiC fiber-reinforced SiC composites with a BN interphase are proposed for use as leading edge structures of hypersonic vehicles. The durability of these materials under hypersonic flight conditions is therefore of interest. Thermogravimetric analysis was used to characterize the oxidation kinetics of both the constituent fibers and composite coupons at four temperatures: 816, 1149, 1343, and 1538 C (1500, 2100, 2450, and 2800 F) and in oxygen partial pressures between 5% and 0.1% (balance argon) at 1 atm total pressure. One edge of the coupons was ground off so the effects of oxygen ingress into the composite could be monitored by post-test SEM and EDS. Additional characterization of the oxidation products was conducted by XPS and TOF-SIMS. Under most conditions, the BN oxidized rapidly, leading to the formation of borosilicate glass. Rapid initial oxidation followed by volatilization of boria lead to protective oxide formation and further oxidation was slow. At 1538C in 5% oxygen, both the fibers and coupons exhibited borosilicate glass formation and bubbling. At 1538C in 0.1% oxygen, active oxidation of both the fibers and the composites was observed leading to rapid SiC degradation. BN oxidation at 1538C in 0.1% oxygen was not significant.
Opila, Elizabeth J.↗
The NASA MSFC Electrostatic Levitation (ESL) Laboratory: Summary of Capabilities, Recent Upgrades, and Future Work
The NASA Marshall Space Flight Center (MSFC) electrostatic levitation (ESL) laboratory has a long history of providing materials research and thermophysical property data. A summary of the labs capabilities, recent upgrades, and ongoing and future work will be provided. The laboratory has recently added two new capabilities to its main levitation chamber: a rapid quench system and an oxygen control system. The rapid quench system allows samples to be dropped into a quench vessel that can be filled with a low melting point material, such as a gallium or indium alloy. Thereby allowing rapid quenching of undercooled liquid metals. The oxygen control system consists of an oxygen sensor, oxygen pump, and a control unit. The sensor is a potentiometric device that determines the difference in oxygen activity between two gas compartments separated by an electrolyte, which is yttria-stabilized zirconia. The pump utilizes coulometric titration to either add or remove oxygen. The system is controlled by a desktop control unit, which can also be accessed via a computer. This system allows the oxygen partial pressure within the vacuum chamber to be measured and controlled, theoretically in the range from 10-36 to 100 bar. The ESL laboratory also has an emissometer, called the High-Temperature Emissivity Measurement System (HiTEMS). This system measures the spectral emissivity of materials from 600degC to 3,000degC. The system consists of a vacuum chamber, a black body source, and a Fourier Transform Infrared Spectrometer (FTIR). The system utilizes optics to swap the signal between the sample and the black body. The system was originally designed to measure the hemispherical spectral emissivity of levitated samples, which are typically 2.5mm spheres. Levitation allows emissivity measurements of molten samples, but more work is required to develop this capability. The system is currently setup measure the near-normal spectral emissivity of stationary samples, which has been used to take measurements of ablative materials, rocket nozzle coating materials, and materials for spacecraft instruments.
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 Partial Pressure on the Surface Tension of Liquid Nickel
The NASA Marshall Space Flight Center's electrostatic levitation (ESL) laboratory has been recently upgraded with an oxygen partial pressure controller. This system allows the oxygen partial pressure within the vacuum chamber to be measured and controlled, theoretically in the range from 10‐36 to 100 bar. The oxygen control system installed in the ESL laboratory's main chamber consists of an oxygen sensor, oxygen pump, and a control unit. The sensor is a potentiometric device that determines the difference in oxygen activity in two gas compartments (inside the chamber and the air outside of the chamber) separated by an electrolyte, which is yttria‐stabilized zirconia. The pump utilizes coulometric titration to either add or remove oxygen. The system is controlled by a desktop control unit, which can also be accessed via a computer. The controller performs temperature control for the sensor and pump, PID-based current loop, and a control algorithm. Oxygen partial pressure has been shown to play a significant role in the surface tension of liquid metals. Oxide films or dissolved oxygen may lead to significant changes in surface tension. The effects of oxygen partial pressure on the surface tension of undercooled liquid nickel will be analyzed, and the results will be presented. The surface tension will be measured at several different oxygen partial pressures while the sample is undercooled. Surface tension will be measured using the oscillating drop method. While undercooled, each sample will be oscillated several times consecutively to investigate how the surface tension behaves with time while at a particular oxygen partial pressure.
SanSoucie, Michael P.↗
Monatomic Oxygen Makes Materials Biocompatible
Treatment with monatomic oxygen activates surfaces of biomedical and biotechnical materials without adversely affecting properties of bulk and without introducing toxic or otherwise dangerous solvent residues. Treatment used to create carpetlike texture increasing surface area and encouraging cells to adhere and grow. On silicone tubing for vascular implants, carpet surface improves acceptance by body. On polymer beads and vessels, surface increases effectiveness of growing, storing, and separating cell cultures. Monatomic oxygen relatively abundant in upper atmosphere of Earth, thus treatments carried out on Space Shuttle missions. Alternatively, one of several high-energy neutral-beam devices used in terrestrial laboratories.
Spaulding, Glenn↗
"The Evolution of Photosynthesis and the Transition from an Anaerobic to an Aerobic World"
This project was focused on elucidating the evolution of photosynthesis, in particular the evolutionary developments that preceded and accompanied the transition from anoxygenic to oxygenic photosynthesis. Development of this process has clearly been of central importance to evolution of life on Earth. Photosynthesis is the mechanism that ultimately provides for the energy needs of most surface-dwelling organisms. Eukaryotic organisms are absolutely dependent on the molecular oxygen that has been produced by oxygenic photosynthesis. In this project we have employed a multidisciplinary approach to understand some of the processes that took place during the evolution of photosynthesis. In this project, we made excellent progress in the overall area of understanding the origin and evolution of photosynthesis. Particular progress has been made on several more specific research questions, including the molecular evolutionary analysis of photosynthetic components and biosynthetic pathways (2,3, 5, 7, 10), as well as biochemical characterization of electron transfer proteins related to photosynthesis and active oxygen protection (4,6,9). Finally, several review and commentary papers have been published (1, 8, 1 1). A total of twelve publications arose out of this grant, references to which are given below. Some specific areas of progress are highlighted and discussed in more detail.
Blankenship, Robert E.↗
Isothermal Microcalorimetric Evaluation of Compatibility of Proposed Injector Materials with High-Test Hydrogen Peroxide Propellant
High-test hydrogen peroxide (HTP) is receiving renewed interest as a monopropellant and as the oxidizer for bipropellant systems. HTP is hydrogen peroxide in concentrations ranging from 70 to 98%. All surfaces wetted by HTP must be evaluated for compatibility with the fluid. In the case of tanks, lines and valves compatibility is required to preserve the HTP oxygen and energy content and to avoid overpressurization due to decomposition. With injectors and regenerative cooling passages shorter exposure time reduces these concerns. However, phase changes from fluid to gas impact heat transfer and become the dominant compatibility concern. Isothermal microcalorimetry (IMC) provides a convenient and reproducible means to observe the decomposition of HTP when exposed to structural materials and therefore the compatibility of those materials'. The instrument provides heat flow values in terms of watts that may be converted to a reaction rate given the heat of reaction for the decomposition of hydrogen peroxide. These values are then converted to percent active oxygen loss per week (%AOL/wk) to preserve an earlier convention for quantifying HTP compatibility. Additionally, qualitative designations of compatibility have been assigned to these values. This scheme consists of four classes with Class 1 being the most compatible. While historical compatibility data is available its current applicability is in question due to subtle changes in the compositions of both HTP and structural materials. Trace levels of molecules can have significant influence on compatibility. Therefore representative samples of materials must be evaluated with current HTP formulations. In this work seven materials were selected for their strength characteristics at high temperature as expected in a HTP injector. The materials were then evaluated by IMC for HTP compatibility.
Gostowski, Rudy↗
Sample selection and preservation techniques for the Mars sample return mission
It is proposed that a miniaturized electron spin resonance (ESR) spectrometer be developed as an effective, nondestructivew sample selection and characterization instrument for the Mars Rover Sample Return mission. The ESR instrument can meet rover science payload requirements and yet has the capability and versatility to perform the following in situ Martian sample analyses: (1) detection of active oxygen species, and characterization of Martian surface chemistry and photocatalytic oxidation processes; (2) determination of paramagnetic Fe(3+) in clay silicate minerals, Mn(2+) in carbonates, and ferromagnetic centers of magnetite, maghemite and hematite; (3) search for organic compounds in the form of free radicals in subsoil, and detection of Martian fossil organic matter likely to be associated with carbonate and other sedimentary deposits. The proposed instrument is further detailed.
Tsay, Fun-Dow↗