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At least 91 records · Page 5

Lunar Metal Oxide Electrolysis with Oxygen and Photovoltaic Array Production Applications

This paper presents the results of a Marshall Space Flight Center funded effort to conduct an experimental demonstration of the processing of simulated lunar resources by the molten oxide electrolysis (MOE) process to produce oxygen and metal from lunar resources to support human exploration of space. Oxygen extracted from lunar materials can be used for life support and propellant, and silicon and metallic elements produced can be used for in situ fabrication of thin-film solar cells for power production. The Moon is rich in mineral resources, but it is almost devoid of chemical reducing agents, therefore, molten oxide electrolysis, MOE, is chosen for extraction, since the electron is the most practical reducing agent. MOE was also chosen for following reasons. First, electrolytic processing offers uncommon versatility in its insensitivity to feedstock composition. Secondly, oxide melts boast the twin key attributes of highest solubilizing capacity for regolith and lowest volatility of any candidate electrolytes. The former is critical in ensuring high productivity since cell current is limited by reactant solubility, while the latter simplifies cell design by obviating the need for a gas-tight reactor to contain evaporation losses as would be the case with a gas or liquid phase fluoride reagent operating at such high temperatures. In the experiments reported here, melts containing iron oxide were electrolyzed in a low temperature supporting oxide electrolyte (developed by D. Sadoway, MIT). The production of oxygen and reduced iron were observed. Electrolysis was also performed on the supporting electrolyte with JSC-1 Lunar Simulant. The cell current for the supporting electrolyte alone is negligible while the current for the electrolyte with JSC-1 shows significant current and a peak at about -0.6 V indicating reductive reaction in the simulant.

Curreri, P. A.↗

Toxic Hazards Research Unit

The activities of the Toxic Hazards Research Unit (THRU) for the period of June 1970 through May 1971 reviewed. Modification of the animal exposure facilities primarily for improved human safety but also for experimental integrity and continuity are discussed. Acute toxicity experiments were conducted on hydrogen fluoride (HF), hydrogen chloride (HCl), nitrogen dioxide (NO2), and hydrogen cyanide (HCN) both singly and in combination with carbon dioxide (CO). Additional acute toxicity experiments were conducted on oxygen difluoride (OF2) and chlorine pentafluoride (ClF5). Subacute toxicity studies were conducted on methylisobutylketone and dichloromethane (methylene dichloride). The interim results of further chronic toxicity experiments on monomethylhydrazine (MMH) are also described.

Macewen, J. D.↗

Teflon lubrication of liquid oxygen turbopump bearings

Ball bearings with glass fiber reinforced Teflon ball retainers from hot-fired liquid oxygen turbopumps were analyzed by X-ray photoelectron spectroscopy to determine the extent of Teflon transfer and/or chemical reaction at the bearing surface. No Teflon, but metal fluorides could be found on the metal surface. This indicates that Teflon decomposes and reacts with the bearing steel to form fluorides. Hence, Teflon does not appear to function directly as a lubricant under these operating conditions.

Naerheim, Y.↗

Utilization of oxygen difluoride for syntheses of fluoropolymers

The reaction oxygen difluoride, OF2, with ethylenically unsaturated fluorocarbon compounds is examined. Depending upon the fluorocarbon material and reaction conditions, OF2 can chain extend fluoropolyenes, convert functional perfluorovinyl groups to acyl fluoride and/or epoxide groups, and act as a monomer for an addition type copolymerization with diolefins.

Toy, M. S.↗

Indium Tin Oxide-Magnesium Fluoride Co-Deposited Films for Spacecraft Applications

Highly transparent coatings with a maximum sheet resistivity between 10(exp 8) and 10(exp 9) ohms/square are desired to prevent charging of solar arrays for low Earth polar orbit and geosynchronous orbit missions. Indium tin oxide (ITO) and magnesium fluoride (MgF2) were ion beam sputter co-deposited onto fused silica substrates and were evaluated for transmittance, sheet resistivity and the effects of simulated space environments including atomic oxygen (AO) and vacuum ultraviolet (VUV) radiation. Optical properties and sheet resistivity as a function of MgF2 content in the films will be presented. Films containing 8.4 wt.% MgF2 were found to be highly transparent and provided sheet resistivity in the required range. These films maintained a high transmittance upon exposure to AO and to VUV radiation, although exposure to AO in the presence of charged species and intense electromagnetic radiation caused significant degradation in film transmittance. Sheet resistivity of the as-fabricated films increased with time in ambient conditions. Vacuum beat treatment following film deposition caused a reduction in sheet resistivity. However, following vacuum heat treatment, sheet resistivity values remained stable during storage in ambient conditions.

Dever, Joycer A.↗

Erosion Data from the MISSE 8 Polymers Experiment After 2 Years of Space Exposure on the International Space Station

The Polymers Experiment was exposed to the low Earth orbit (LEO) space environment for 2.14 and 2.0 years as part of the Materials International Space Station Experiment 8 (MISSE 8) and the Optical Reflector Materials Experiment-III (ORMatE-III), respectively. The experiment contained 42 samples, which were flown in either ram, wake, or zenith orientations. The primary objective was to determine the effect of solar exposure on the atomic oxygen erosion yield (Ey) of fluoropolymers. This paper provides an overview of the experiment with details on the polymers flown, the characterization techniques used, the atomic oxygen fluence for each exposure orientation, and the LEO Ey results. The Ey values for the fluoropolymers range from 1.45 x 10(exp -25) cm(exp 3)/atom for white Tedlar Registered Trademark (polyvinyl fluoride with white titanium dioxide pigment) flown in the ram orientation to 6.32 x 10(exp -24) cm(exp 3)/atom for aluminized-Teflon Registered Trademark fluorinated ethylene propylene (Al-FEP) flown in the zenith orientation. Erosion yield data for FEP flown in ram, wake and zenith orientations are compared, and the Ey was found to be highly dependent on orientation, hence environmental exposure. Teflon FEP had an order of magnitude higher Ey when flown in the zenith direction (6.32 x10(exp -24) cm(exp3)/atom) as compared to the ram direction (2.37 x 10(exp -25) cm(exp 3)/atom). The Ey of FEP was found to increase with a direct correlation to the solar exposure/AO fluence ratio showing the effect of solar radiation and/or heating due to solar exposure on FEP erosion. In addition, back-surface carbon painted FEP (C-FEP) flown in the zenith orientation had a significantly higher Ey than clear FEP or Al-FEP further indicating that heating has a significant impact on the erosion of FEP, particularly in the zenith orientation.

Solar radiation↗

Investigating Dual Electrospinning as a Means of Enhancing Passive Thermal Control Coatings for Cryogenic Propellant Storage in Extraterrestrial Environments

Passive thermal control is necessary as space exploration becomes increasingly widespread. Materials with superior optical properties (high solar reflectance and infrared emittance) are critical for passive thermal control because they can reject most of the incident solar radiation and promote thermal emission from cryogenic propellant storage tanks, enabling the extraterrestrial storage of cryogens. We have demonstrated in previous studies that electrospun nanofibers exhibit exceptional optical properties, offering significant benefits for passive radiative cooling in space. Particularly, electrospun polyvinylidene fluoride-co-hexafluoropropylene PVDF-HFP nanofibers demonstrate exceptionally high solar reflectance (>99%) and strong thermal emittance (measured at ~300 K). However, they exhibit nanostructural changes in the presence of atomic oxygen, which is prevalent in Low Earth Orbit. This study focuses on creating a unique blend of polymeric (PVDF-HFP) and ceramic-based (silica) nanofibers by leveraging the chemical stability and atomic oxygen resistance of silica, using the dual electrospinning manufacturing method. This approach aims to preserve the structural properties of the polymeric counterpart without compromising its optical performance, thereby providing an innovative method for manufacturing environmentally resilient passive thermal control nanofibers with desirable optical and thermal control functionalities for extraterrestrial storage of cryogenic propellants.

Chieloka Ibekwe↗

Direct Mapping of Fluorine in Cation Disordered Rocksalt Cathodes

Cation-disordered rocksalt (DRX) oxides are promising candidates as next-generation cathodes for lithium-ion batteries. Partial fluorination of the DRX oxides enhances their cyclability. However, the lattice position, concentration, and spatial distribution of fluorine within DRX lattices remain elusive. Here, in this work, we use atom location by channeling-enhanced microanalysis, energy-dispersive X-ray spectroscopy, electron energy loss spectroscopy, and integrated differential phase contrast imaging in a scanning transmission electron microscope to gain atomic-level insights into DRX with nominal composition of Li 1.2 Mn 0.7 Ti 0.1 O 1.7 F 0.3 and Li 1.15 Ni 0.45 Ti 0.3 Mo 0.1 O 1.85 F 0.15 . We reveal that fluorine substitutes oxygen in the DRX lattices. The O/F ratio in terms of O+F = 2 is in the range from 1.92:0.08 to 1.82:0.18. Spatially, fluorine is distributed in the proximity of the Li-rich regions but distinct from lithium fluoride. Additionally, we observe that incorporation of fluorine in the DRX lattice induces a larger variation in cation–anion separation. These observations provide insight into the guided design of oxyfluoride DRX cathodes for high-performance batteries.

(S)TEM↗

Non-Innocent Role of the Ceria Support in Pd-Catalyzed Halophenol Hydrodehalogenation

The hydrodehalogenation (HDH) of halophenols is efficiently catalyzed by palladium supported on high-surface ceria (Pd/CeO2) under mild conditions (35 °C, 1 atm H2). A combination of NMR, diffuse reflectance infrared Fourier transform spectroscopy, Raman spectroscopy, and XPS studies and HDH kinetics of substituted halobenzenes suggests that the reaction proceeds mainly via a sequence of dissociative adsorption of phenolic hydroxyl onto the support, oxidative addition of the C–halogen bond to Pd, and reductive elimination to give phenol and hydrogen halide. The dissociative adsorption of the -OH group onto oxygen vacancies of the ceria support results in an electron-rich intermediate that facilitates the turnover-limiting reductive elimination step. In contrast, the direct pathway catalyzed by Pd without dissociative adsorption of the reactants on the support takes place at a slower rate. The mechanistic insights gained in this study were used to modify the reaction conditions for enabling HDH of recalcitrant halides such as fluorides and iodides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Intercalation of Lithium in Pitch-Based Graphitized Carbon Fibers Chemically Modified by Fluorine: Soft Carbon With or Without an Oxide Surface

The effects of carbon structure and surface oxygen on the carbon's performance as the anode in lithium-ion battery were studied. Two carbon materials were used for the electrochemical tests: soft carbon made from defluorination of graphite fluoride, and the carbon precursor from which the graphite fluoride was made. In this research the precursor was graphitized carbon fiber P-100. It was first fluorinated to form CF(0.68), then defluorinated slowly at 350 to 450 C in bromoform, and finally heated in 1000 C nitrogen before exposed to room temperature air, producing disordered soft carbon having basic surface oxides. This process caused very little carbon loss. The electrochemical test involved cycles of lithium intercalation and deintercalation using C/saturated LiI-50/50 (vol %) EC and DMC/Li half cell. The cycling test had four major results. (1) The presence of a basic oxide surface may prevent solvent from entering the carbon structure and therefore prolong the carbon's cycle life for lithium intercalation-deintercalation. (2) The disordered soft carbon can store lithium through two different mechanisms. One of them is lithium intercalation. which gives the disordered carbon an electrochemical behavior similar to its more ordered graphitic precursor. The other is unknown in its chemistry, but is responsible for the high-N,oltage portion (less than 0.3V) of the charge-discharge curve. (3) Under certain conditions, the disordered carbon can store more lithium than its precursor. (4) These sample and its precursor can intercalate at 200 mA/g. and deintercalate at a rate of 2000 mA/g without significant capacity loss.

Hung, Ching-Chen↗

Applications Of Graphite Fluoride Fibers In Outer Space

Report characterizes graphite fluoride fibers made from commercially available graphitized carbon fibers and discusses some potential applications of graphite fluoride fibers in outer space. Applications include heat-sinking printed-circuit boards, solar concentrators, and absorption of radar waves. Other applications based on exploitation of increased resistance to degradation by atomic oxygen, present in low orbits around Earth.

Hung, Ching-Cheng↗

Hydrogen-oxygen proton-exchange membrane fuel cells and electrolyzers

Hydrogen-oxygen SPE fuel cells and SPE electrolyzers (products of Hamilton Standard) both use a Proton-Exchange Membrane (PEM) as the sole electrolyte. The SPE cells have demonstrated a ten year life capability under load conditions. Ultimate life of PEM fuel cells and electrolyzers is primarily related to the chemical stability of the membrane. For perfluorocarbon proton-exchange membranes an accurate measure of the membrane stability is the fluoride loss rate. Millions of cell hours have contributed to establishing a relationship between fluroride loss rates and average expected ultimate cell life. Several features were introduced into SPE fuel cells and SPE electrolyzers such that applications requiring greater than or equal to 100,000 hours of life can be considered. Equally important as the ultimate life is the voltage stability of hydrogen-oxygen fuel cells and electrolyzers. Here again the features of SPE fuel cells and SPE electrolyzers have shown a cell voltage stability in the order of 1 microvolt per hour. That level of stability were demonstrated for tens of thousands of hours in SPE fuel cells at up to 500 amps per square foot (ASF) current density. The SPE electrolyzers have demonstrated the same at 1000 ASF. Many future extraterrestrial applications for fuel cells require that they be self recharged. To translate the proven SPE cell life and stability into a highly reliable extraterrestrial electrical energy storage system, a simplification of supporting equipment is required. Static phase separation, static fluid transport and static thermal control will be most useful in producting required system reliability. Although some 200,000 SPE fuel cell hours were recorded in earth orbit with static fluid phase separation, no SPE electrolyzer has, as yet, operated in space.

Baldwin, R.↗

Hydrogen-oxygen proton-exchange membrane fuel cells and electrolyzers

Hydrogen-oxygen solid polymer electrolyte (SPE) fuel cells and SPE electrolyzers (products of Hamilton Standard) both use a Proton-Exchange Membrane (PEM) as the sole electrolyte. These solid electrolyte devices have been under continuous development for over 30 years. This experience has resulted in a demonstrated ten-year SPE cell life capability under load conditions. Ultimate life of PEM fuel cells and electrolyzers is primarily related to the chemical stability of the membrane. For perfluorocarbon proton exchange membranes an accurate measure of the membrane stability is the fluoride loss rate. Millions of cell hours have contributed to establishing a relationship between fluoride loss rates and average expected ultimate cell life. This relationship is shown. Several features have been introduced into SPE fuel cells and SPE electrolyzers such that applications requiring greater than or equal to 100,000 hours of life can be considered. Equally important as the ultimate life is the voltage stability of hydrogen-oxygen fuel cells and electrolyzers. Here again the features of SPE fuel cells and SPE electrolyzers have shown a cell voltage stability in the order of 1 microvolt per hour. That level of stability has been demonstrated for tens of thousands of hours in SPE fuel cells at up to 500 amps per square foot (ASF) current density.

Baldwin, R.↗

Structures of fluoride containing aluminosilicate low activity nuclear waste glasses: A molecular dynamics simulations study

Fluorine and other halides commonly exist in nuclear waste forms, and due to their volatile nature, halide retention poses an issue affecting waste loading during vitrification. The compositional effect on fluorine incorporation in aluminosilicate glasses is investigated through molecular dynamics simulations. Oxygen and fluorine coordination numbers around glass former and modifier cations, bond angle distributions, and medium range structure features such as Q n distributions, ring size distributions and neutron diffraction structure factors were calculated. It was found that fluorine has higher preference to bond to Ca 2+ than to Na + , both in the melt and the glass, and there is no Si-F bond formation in the glass but they do exist in the melt. Consequently, CaO for Na 2 O substitution can be an effective way to help fluorine retention without significantly changing the glass chemistry. Furthermore, these results thus provide insights on fluorine incorporation in the aluminosilicate nuclear waste glasses and the strategy on how to improve fluorine retention both in the glass and the melt.

36 MATERIALS SCIENCE↗

Facility and Methods Developed for Simulated Space Vacuum Ultraviolet Exposure Testing of Polymer Films

Vacuum ultraviolet (VUV) radiation of wavelengths between 115 and 200 nm produced by the Sun in the space environment can degrade polymer films, producing changes in their optical, mechanical, and chemical properties. These effects are particularly important for thin polymer films being considered for ultralightweight space structures, because, for most polymers, VUV radiation is absorbed in a thin surface layer. The NASA Glenn Research Center has developed facilities and methods for long-term ground testing of polymer films to evaluate space environmental VUV radiation effects. VUV exposure can also be used as part of combined or sequential simulated space environmental exposures to determine combined damaging effects with other aspects of the space environment, which include solar ultraviolet radiation, solar flare x-rays, electron and proton radiation, atomic oxygen (for low-Earth-orbit missions), and temperature effects. Because the wavelength sensitivity of VUV damage is not well known for most materials, Glenn's VUV facility uses a broad-spectrum deuterium lamp with a magnesium fluoride window that provides output between 115 and 200 nm. Deuterium lamps of this type were characterized by the National Institute of Standards and Technology and through measurements at Glenn. Spectral irradiance measurements show that from approximately 115 to 160 nm, deuterium lamp irradiance can be many times that of air mass zero solar irradiance, and as wavelength increases above approximately 160 nm, deuterium lamp irradiance decreases in comparison to the Sun. The facility is a cryopumped vacuum chamber that achieves a system pressure of approximately 5310(exp -6) torr. It contains four individual VUV-exposure compartments in vacuum, separated by water-cooled copper walls to minimize VUV radiation and any sample contamination cross interactions between compartments. Each VUV-exposure compartment contains a VUV deuterium lamp, a motor-controlled sample stage coupled with a moveable cesium iodide VUV phototube, and two thermocouples for temperature measurement. The vacuum chamber and exterior equipment is shown. Each VUV lamp is located at the top of the chamber with its projection-tube pushed through an O-ring compression fitting. The lamp assemblies are located on ports that can be isolated from the rest of the vacuum chamber, permitting maintenance or replacement of the lamps without breaking vacuum in the main chamber where the samples are located. A view of two of the four interior VUV-exposure compartments, including the moveable sample stages and detector holders is also shown. Glenn is using this facility to support testing of Next Generation Space Telescope sunshield materials that is being led by the NASA Goddard Space Flight Center and to develop an understanding of the wavelength, intensity, and temperature dependence of VUV-induced polymer degradation.

Dever, Joyce A.↗

Pilot Plant Makes Oxygen Difluoride

Pilot plant makes oxygen difluoride highly-energetic, space-storable oxidizer not made commercially. Designed to handle reactants, product, and byproduct, most of which highly reactive, corrosive, and toxic. Oxygen difluoride evolves continuously from reactor containing potassium hydroxide in water at 10 degree C. Collection tanks alternated; one filled while other drained to storage cylinder. Excess OF2 and F2 dissipated in combustion of charcoal in burn barrel. Toxic byproduct, potassium fluoride, reacted with calcium hydroxide to form nontoxic calcium fluoride and to regenerate potassium hydroxide. Equipment processes toxic, difficult-to-make substance efficiently and safely.

Humphrey, Marshall F.↗

Investigation of $\gamma$-irradiated polyvinylidene fluoride and its acute toxicity

Polyvinylidene fluoride (PVDF) is an industrial polymer with many applications. The EPR spectrum of polyvinylidene fluoride (PVDF) irradiated by γ-rays at low temperature (-196°C) provides evidence for the presence of radicals formed by loss of a fluorine atom from PVDF, and polyenyl radicals. Polyenyl radicals dominate in the polymer irradiated at room temperature. Peroxide radicals formed as a result of oxidation of primary free radicals by atmospheric oxygen are observed in the EPR spectrum of a polymer irradiated in air, or when air is introduced to a polymer irradiated in a vacuum. Carbonization and oxidation of γ-irradiated PVDF were observed in the XPS spectrum. A model for polymer degradation based on correlated G3(MP2) molecular orbital theory electronic structure calculations is described in this report. The presence of HF in the products and a low yield of products with the composition CxFyHz indicate the absence of noticeable thermal destruction of the main polymer chain upon heating to 220°C of both the initial and γ-irradiated PVDF. Although any HF released during the PVDF dehydrofluorination would be toxic, a study of the acute toxicity of γ-irradiated PVDF showed that the polymer does not exhibit toxicity after a single intragastric route of administration to mice.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Experimental investigations of low-energy (4 to 40 eV) collisions of O(-)(P2) ions and O(P3) atoms with surfaces

Using a newly-developed, magnetically confined source, low-energy, ground state oxygen negative ions and neutral atoms are generated. The energy range is variable, and atom and neutrals have been generated at energies varying from 2 eV to 40 eV and higher. It was found that the interaction of these low-energy species with a solid magnesium fluoride target leads to optical emissions in the (at least) visible and infrared regions of the spectrum. Researchers describe y details of the photodetachment source, and present spectra of the neutral and ion glows in the wavelength range 250 to 850 nm (for O(-)) and 600 to 850 nm (for O), and discuss the variability of the emissions for incident energies between 4 and 40 eV.

Chutjian, A.↗