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All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Relaxation Dynamics and Ion Conduction of Poly(Ethylene Carbonate/Ethylene Oxide) Copolymer-Based Electrolytes

Poly(ethylene carbonate/ethylene oxide) P(EC/EO) copolymer was synthesized from EC monomer as a new matrix component of solid polymer electrolytes (SPEs), and the correlation between polymer dynamics and ionic conductivity in the P(EC/EO)-based SPEs at various lithium salt weight fractions (w Li ) was investigated by dielectric spectroscopy, rheology, and molecular dynamics (MD) simulations. With the addition of lithium salt, the molecular motions at various scales (i.e., from local to segmental and global motion scales) were found to change as follows: (i) the local motion of P(EC/EO) was slightly accelerated, and at w Li ≥ 0.22, it was separated into two relaxation modes, one faster and the other slower than that of P(EC/EO), (ii) the segmental motion of P(EC/EO) became significantly slower with the addition of lithium salt, and (iii) the global terminal relaxation became slightly slower with the increase of w Li . Thus, the motion of P(EC/EO) at various scales in SPEs changed with different trends with increasing lithium salt. It was also found that the temperature dependence of the ionic conductivity was described by a Vogel–Fulcher–Tammann-type function, which was correlated with the segmental motion, as is known in other SPE systems. Furthermore, from MD simulations, lithium ions are coordinated with the EC units more likely and with a closer distance than EO units in P(EC/EO), and the coordination number of oxygens around one lithium ion was estimated as 6–7 at the distance of 0.30 nm. Here, these results suggest that the coordination structure of the oxygens around the lithium ion is slightly disrupted due to the presence of EC units compared to the chelating structure of pure PEO electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Non-Intrusive Measurements Using Femtosecond Laser in Atmospheric Pressure Plasma Jet

Femto-second (fs) lasers offer state-of-the art non-intrusive diagnostic capabilities in plasma flow environments. The diagnostics in plasma flows using a fs-laser that are relevant to this proposal include Two-photon Absorption Laser Induced Fluorescence (TALIF) for measuring the number density of an atomic species, and Femto-second Laser Electronic Excitation Tagging (FLEET) for performing velocity measurements in plasma flows. Various aspects of these diagnostics using fs-lasers are still an active domain of research. The TALIF technique has been used to measure the number density of atomic species in various plasma flow environments like atmospheric pressure plasma jet (APPJ) and arc-jet flows. This technique utilizes a fs-laser to excite an atomic species and the subsequent relaxation process through fluorescence is recorded to make measurements. A narrow band-pass filter is used to isolate the fluorescence signal that is in the infra-red regime. However, broad-band background emissions can potentially pass through the filter and induce noise in the TALIF signal. Particularly, arc-jet plasma flows inherently contain background emissions. In such plasma flow environments, in addition to the filter, the background-subtraction technique will play an important role in reducing the noise that is induced in the number density measurements using TALIF. The proposed research focuses on evaluating the effectiveness of a background-subtraction technique by measuring atomic oxygen using a femtosecond (fs) TALIF in APPJ with induced background emissions and comparing measurements obtained without inducing the emissions. Therefore, by quantifying the changes in the signal-to-noise ratio caused by a background-subtraction technique applied for APPJ, it will enable a better understanding of the uncertainties in the background subtracted fs-TALIF measurements for arc-jet plasma flows. In addition to this, FLEET will be used to obtain velocity in the APPJ, and the impact of background emissions will be analyzed. Under this effort, the experimenters and research personnel will gain the technical know-how in the operational and theoretical aspects of the advanced fs-laser-based diagnostic techniques. The knowledge gained in this process will then also directly be applied to a separate ONR funded project at the Aerodynamics Research Center (ARC), UT Arlington, related to arc-jet flow characterization.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Effect of Substrate Temperature on the Electrochemical and Supercapacitance Properties of Pulsed Laser-Deposited Titanium Oxynitride Thin Films

Electrocatalytically active titanium oxynitride (TiNO) thin films were fabricated on commercially available titanium metal plates using a pulsed laser deposition method for energy storage applications. The elemental composition and nature of bonding were analyzed using X-ray photoelectron spectroscopy (XPS) to reveal the reacting species and active sites responsible for the enhanced electrochemical performance of the TiNO electrodes. Symmetric supercapacitor devices were fabricated using two TiNO working electrodes separated by an ion-transporting layer to analyze their real-time performance. The galvanostatic charge–discharge studies on the symmetric cell have indicated that TiNO films deposited on the polycrystalline titanium plates at lower temperatures are superior to TiNO films deposited at higher temperatures in terms of storage characteristics. For example, TiNO films deposited at 300 °C exhibited the highest specific capacity of 69 mF/cm 2 at 0.125 mA/cm 2 with an energy density of 7.5 Wh/cm 2 . The performance of this supercapacitor (300 °C TiNO) device is also found to be ~22% better compared to that of a 500 °C TiNO supercapacitor with a capacitance retention ability of 90% after 1000 cycles. Furthermore, the difference in the electrochemical storage and capacitance properties is attributed to the reduced leaching away of oxygen from the TiNO films by the Ti plate at lower deposition temperatures, leading to higher oxygen content in the TiNO films and, consequently, a high redox activity at the electrode/electrolyte interface.

30 DIRECT ENERGY CONVERSION↗
NASA NTRS1991

Isotopic compositions of carbonates and organic carbon from upper Proterozoic successions in Namibia: stratigraphic variation and the effects of diagenesis and metamorphism

The carbon isotope geochemistry of carbonates and organic carbon in the late Proterozoic Damara Supergroup of Namibia, including the Nama, Witvlei, and Gariep groups on the Kalahari Craton and the Mulden and Otavi groups on the Congo Craton, has been investigated as an extension of previous studies of secular variations in the isotopic composition of late Proterozoic seawater. Subsamples of microspar and dolomicrospar were determined, through petrographic and cathodoluminescence examination, to represent the "least-altered" portions of the rock. Carbon-isotopic abundances in these phases are nearly equal to those in total carbonate, suggesting that 13C abundances of late Proterozoic fine-grained carbonates have not been significantly altered by meteoric diagenesis, although 18O abundances often differ significantly. Reduced and variable carbon-isotopic differences between carbonates and organic carbon in these sediments indicate that isotopic compositions of organic carbon have been altered significantly by thermal and deformational processes, likely associated with the Pan-African Orogeny. Distinctive stratigraphic patterns of secular variation, similar to those noted in other, widely separated late Proterozoic basins, are found in carbon-isotopic compositions of carbonates from the Nama and Otavi groups. For example, in Nama Group carbonates delta 13C values rise dramatically from -4 to +5% within a short stratigraphic interval. This excursion suggests correlation with similar excursions noted in Ediacaran-aged successions of Siberia, India, and China. Enrichment of 13C (delta 13C> +5%) in Otavi Group carbonates reflects those in Upper Riphean successions of the Akademikerbreen Group, Svalbard, its correlatives in East Greenland, and the Shaler Group, northwest Canada. The widespread distribution of successions with comparable isotopic signatures supports hypotheses that variations in delta 13C reflect global changes in the isotopic composition of late Proterozoic seawater. Within the Damara basin, carbon-isotopic compositions of carbonates provide a potentially useful tool for the correlation of units between the Kalahari and Congo cratons. Carbonates depleted in 13C were deposited during and immediately following three separate glacial episodes in Namibia. The correspondence between ice ages and negative delta 13C excursions may reflect the effects of lowered sea levels; enhanced circulation of deep, cold, O2-rich seawater; and/or the upwelling of 13C-depleted deep water. Iron-formation is additionally associated with one of the glacial horizons, the Chuos tillite. Carbon-13 enriched isotopic abundances in immediately pre-glacial carbonates suggest that oceanographic conditions favored high rates of organic burial. It is likely that marine waters were stratified, with deep waters anoxic. A prolonged period of ocean stratification would permit the build-up of ferrous iron, probably from hydrothermal sources. At the onset of glaciation, upwelling would have brought 13C-depleted and iron-rich deep water onto shallow shelves where contact with cold, oxygenated surface waters led to the precipitation of ferric iron.

NASA Program Exobiology↗
NASA NTRS1959

Interactions Between Oxygen and Nitrogen: O[Single Bond]N, O[Single Bond]N (sub 2), and O (sub 2)[Single Bond]N (sub 2)

Potential energy curves for 0-N interactions corresponding to the X (sup 2) II (sub t/2), X (sup 2) II (sub 3/2), A (sup 2) Eta (sup plus), B (sup 2) II, C (sup 2) II, D (sup 2) Eta (sup plus), E (sup 2) Eta (sup plus), and B prime (sup 2 delta) states of nitric oxide have been calculated from spectroscopic data by the Rydberg- Klein-Rees method. Curves for the (sup 4) II, (sup 2) Eta, (sup 4) Eta, (sup 6) Eta, and (sup 6) II states have been obtained from limited spectroscopic results and from relations derived from approximate quantum-mechanical calculations. Two semi-independent calculations have been made, and are in good agreement with each other. The quantum-mechanical relations also lead to approximate curves for the O[Single Bond]N, and O[Single Bond]N (sub 2) interactions over a limited range. The O (sub 2)[Single Bond]N (sub 2) interaction is consistent with one valid at larger separation distances which has been derived from high-temperature gas viscosity data.

Vanderslice, Joseph T.↗
NASA NTRS1994

Long-term modulation of galactic cosmic radiation and its model for space exploration

As the human exploration of space has received new attention in the United States, studies find that exposure to space radiation could adversely impact the mission design. Galactic Cosmic Radiation (GCR), with its very wide range of charges and energies, is particularly important for a mission to Mars, because it imposes a stiff mass penalty for spacecraft shielding. Dose equivalent versus shielding thickness calculations, show a rapid initial drop on exposure with thickness, but an asymptotic behavior at a higher shielding thickness. Uncertainties in the radiobiology are largely unknown. For a fixed radiation risk, this leads to large uncertainties in shielding thickness for small uncertainties in estimated dose. In this paper we investigate the application of steady-state, spherically-symmetric diffusion-convection theory of solar modulation to individual measurements of differential energy spectra from 1954 to 1989 in order to estimate the diffusion coefficient, kappa(r,t), as a function of time. We have correlated the diffusion coefficient to the Climax neutron monitor rates and show that, if the diffusion coefficient can be separated into independent functions of space and time: kappa(r,t)=K(t) k(sub 0) beta Pk(sub 1) (r), where beta is the particle velocity and P the rigidity, then (i) The time dependent quantity 1/K(t), which is proportional to the deceleration potential, phi(r,t), is linearly related to the Climax neutron monitor counting rate. (ii) The coefficients obtained from hydrogen or helium intensity measurements are the same. (iii) There are different correlation functions for odd and even solar cycles. (iv) The correlation function for the Climax neutron monitor counting rate for given time, t, can be used to estimate mean deceleration parameter phi(t) to within +/- 15% with 90% confidence. We have shown that k(r,t) determined from hydrogen and/or helium data, can be used to fit the oxygen and iron differential energy spectra with a root mean square error of about +/- 10%, and essentially independent of the particle charge or energy. We have also examined the ion chamber and C-14 measurements which allow the analysis to be extended from the year 1906 to 1990. Using this model we have defined reference GCR spectra at solar minimum and solar maximum. These can be used for space exploration studies and provide a quantitative estimate of the error in dose due to changes in GCR intensities.

Badhwan, G. D.↗
NASA NTRS2000

The Proton and Electron Aurora as Seen by Image-FUV and FAST

The Far Ultraviolet (FUV) instrument on IMAGE images the aurora in three different wavelength regions. The Wideband Imaging Camera (WIC) observes the molecular Lyman-Birge-Hopfield (LBH) and atomic Nitrogen emissions at 140-190 nm. The two channels of the Spectrographic Imager (SI) observe the Doppler shifted Lyman Alpha emission of precipitating protons at 121.8 nm (SI 12) and the mostly electron produced emission from oxygen OI at 135.6 nm (SI13). The major advantage of FUV compared to previously flown UV imagers is the simultaneous operation of all three imaging systems without the need for filter changes and the uncertainty of temporal changes of the aurora between exposures. The FAST satellite passes every two hours through FUV images during apogee operations. This enables a comparison between the remotely imaged particle precipitation and the in-situ measurements along the FAST track. The detailed analysis of images from all three systems together with a full simulation of auroral emissions based on in-situ measurements by FAST confirms the laboratory calibrations of FUV. The spatial resolution and image quality of WIC permits the observation of a good correspondence between in-situ and remote measurements of precipitation boundaries. The clear separation between the lower latitude proton precipitation and the more structured higher latitude electron precipitation is obtained with both SI-channels.

Gerard, J.-C.↗
NASA NTRS2000

Solid Lubrication Fundamentals and Applications

This chapter focuses attention on the friction and wear properties of selected solid lubricating films to aid users in choosing the best lubricant, deposition conditions, and operational variables. For simplicity, discussion of the tribological properties of concern is separated into two parts. The first part of the chapter discusses the different solid lubricating films selected for study including commercially developed solid film lubricants: (1) bonded molybdenum disulfide (MoS2), (2) magnetron-sputtered MoS2, (3) ion-plated silver, (4) ion-plated lead, (5) magnetron-sputtered diamondlike carbon (MS DLC), and (6) plasma-assisted, chemical-vapor-deposited diamondlike carbon (PACVD DEC) films. Marked differences in the friction and wear properties of the different films resulted from the different environmental conditions (ultrahigh vacuum, humid air, and dry nitrogen) and the solid film lubricant materials. The second part of the chapter discusses the physical and chemical characteristics, friction behavior, and endurance life of the magnetron-sputtered MoS2 films. The role of interface species and the effects of applied load, film thickness, oxygen pressure, environment, and temperature on the friction and wear properties are considered.

Miyoshi, Kazuhisa↗
DOE OSTI2023

Catalyzed oxidation of IG-110 nuclear graphite by simulated fission products Ag and Pd nanoparticles

To evaluate the stability of nuclear materials in high temperature gas reactors under air ingress conditions, catalytic oxidation of IG-110 graphite by two simulated fission products, metallic Pd and Ag, was studied in oxidative atmosphere and at temperatures up to 1000°C using an integrated furnace, mass spectroscopy and infrared spectroscopy system. Transmission electron microscopy and X-ray diffraction studies show that Pd and Ag nanoparticles were successfully introduced onto powdery IG-110 graphite through an impregnation and subsequent heat-treatment process. The combined mass spectroscopy and infrared spectroscopy methods allow simultaneous analysis of two gaseous products, CO and CO 2 , and separate measurements of activation energy for their formation reactions. It was found that the introduction of Pd or Ag to IG-110 graphite substantially catalyzed the oxidation of graphite, characteristic of decreased onset temperatures for the oxidation of graphite. Moreover, the catalytic effects by Pd and Ag are considerably different based on measured concentration ratios of CO 2 to CO as a function of oxidation temperatures. Ag makes the graphite oxidation commence at approximately 400°C with CO 2 being the dominant product. In contrast, Pd significantly increases the concentration ratio of CO 2 to CO at temperatures higher than approximately 690°C, although it decreases the onset temperature for the oxidation reaction to around 525°C. To understand the catalytic difference, the mechanism of the graphite oxidation was discussed based on the changes of surface oxygen species on Ag and Pd.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
NASA NTRS1987

Regenerative fuel cell study for satellites in GEO orbit

Summarized are the results of a 12-month study to identify high performance regenerative hydrogen-oxygen fuel cell concepts for geosynchronous satellite application. Emphasis was placed on concepts with the potential for high energy density (W-hr/lb) and passive means for water and heat management to maximize system reliability. Both polymer membrane and alkaline electrolyte fuel cells were considered, with emphasis on the alkaline cell because of its high performance, advanced state of development, and proven ability to operate in a launch and space environment. Three alkaline system concepts were studied. The first, the integrated design, utilized a configuration in which the fuel cell and electrolysis cells are alternately stacked inside a pressure vessel. Product water is transferred by diffusion during electrolysis and waste heat is conducted through the pressure wall, thus using completely passive means for transfer and control. The second alkaline system, the dedicated design, uses a separate fuel cell and electrolysis stack so that each unit can be optimized in size and weight based on its orbital operating period. The third design was a dual function stack configuration, in which each cell can operate in both fuel cell and electrolysis mode, thus eliminating the need for two separate stacks and associated equipment. Results indicate that using near term technology energy densities between 46 and 52 W-hr/lb can be achieved at efficiencies of 55 percent. System densities of 115 W-hr/lb are contemplated.

Levy, Alexander↗
NASA NTRS2011

Development of the International Space Station (ISS) Fine Water Mist (FWM) Portable Fire Extinguisher

NASA is developing a Fine Water Mist Portable Fire Extinguisher for use on the International Space Station. The International Space Station presently uses two different types of fire extinguishers: a water foam extinguisher in the Russian Segment, and a carbon dioxide extinguisher in the US Segment and Columbus and Kibo pressurized elements. Changes in emergency breathing equipment make Fine Water Mist operationally preferable. Supplied oxygen breathing systems allow for safe discharge of a carbon dioxide fire extinguisher, without concerns of the crew inhaling unsafe levels of carbon dioxide. But the Portable Breathing Apparatus (PBA) offers no more than 15 minutes of capability, and continued use of hose based supplied oxygen system increases the oxygen content in a fire situation. NASA has developed a filtering respirator cartridge for use in a fire environment. It is qualified to provide up to 90 minutes of capability, and because it is a filtering respirator it does not add oxygen to the environment. The fire response respirator cartridge does not filter carbon dioxide (CO2), so a crew member discharging a CO2 fire extinguisher while wearing this filtering respirator would be at risk of inhaling unsafe levels of CO2. Fine Water Mist extinguishes a fire without creating a large volume of air with reduced oxygen and elevated CO2. From a flight hardware design perspective, the fine water mist fire extinguisher has two major elements: (1) the nozzle and crew interface, and (2) the tank. The nozzle and crew interface has been under development for several years. It has gone through several design iterations, and has been part of more than 400 fire challenge and spray characterizations. The crew and vehicle interface aspects of the design will use the heritage of the CO2 based Portable Fire Extinguisher, to minimize the disruption to the crew and integration impacts to the ISS. The microgravity use environment of the system poses a set of unique design requirements specifically for the tank. The nozzle requirements drive a tank pressure that is 2-5 times higher than any commercially available water mist systems. Microgravity requires deliberate separation of gas and water, facilitated by a bladder, a diaphragm, a piston, or separate tanks. This paper will describe the design details of the tank and the nozzle, and discuss the trade studies that informed the decisions to select the tank and nozzle configuration.

Clements, Anna L.↗
DOE OSTI2025

In anaerobic reactors the microbial community structure depends on feed type, with no “keystone” species tied to COD removal

Two-stage anaerobic digestion (AD) systems provide treatment for high strength wastewater with high stability and performance. Encapsulation technology can intensify AD to facilitate the separation of the solids retention time from the hydraulic retention time (HRT), offering lower HRTs, smaller reactors, and high effluent quality. To support successful deployment, however, the encapsulated community must contain all the needed microorganisms for successful treatment and be flexible enough to treat a variety of wastewaters. Here, a two-stage system was investigated in which microbial cultures were enriched on various high-strength wastewaters in suspended flow-through systems to determine how feed type influenced performance and microbial community structure. The hypothesis was that specific genera, or so-called “keystone species” would positively correlate to organic carbon degradation for a given feed, enabling construction of a well-functioning community for encapsulation. Results showed that the number of total bacteria (as 16S rRNA gene copies) did not correlate to soluble chemical oxygen demand (sCOD) removal, indicating that the community structure and/or members were important for good performance. Results also showed that feed type strongly influenced carbon removal and microbial community structure for 1st-stage fermenting communities, but not 2nd-stage methanogenic communities. In this study, the “core” community members were defined as organisms common to all of either the 1st- or 2nd-stage reactors irrespective of the feed they received and were present in at least 50% of the samples throughout the entire experiment. “Unique” community members were specific to a single feed, and hence, only present in either the 1st- or 2nd-stage reactors receiving that feed. In both 1st- and 2nd-stage communities, only one core genera and no unique genera were positively and significantly correlated to sCOD removal. Verification experiments performed with encapsulated communities showed that organisms identified in flow-through system and correlated with carbon degradation, though not significantly, seemed to be important for performance. Our results suggest that one cannot construct a community containing specific populations in lieu of enrichment. Nevertheless, a single diverse encapsulated anaerobic community should provide good (>80%) carbon removal when fed a variety of influents, if time is provided for enrichment after deployment.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Gas-solid reaction pathway for chlorination of rare earth and actinide metals using hydrogen and chlorine gas

Hydriding and chlorination of buttons of metallic cerium have been tested as a head-end step to separating metal impurities from actinides. The objective here was to achieve complete conversion to chlorides while maintaining high surface area via small particles and open porosity. Hydriding by reaction with 100% H 2 gas at 573 K was successful at reducing cm-scale metal buttons into small particles/fragments. This step was followed by reaction with flowing 99.5% anhydrous Cl 2 gas at temperatures ranging from 423 to 573 K for 60 min. In experiments reported here, up to 92% conversion to cerium chloride was achieved from reacting with the anhydrous chlorine gas. The final chloride product has high porosity coupled with small particle sizes (microns to 1600 μm), which makes it suitable for subsequent purification processes. Higher chlorine concentrations in the gas favor higher conversion to chloride. The optimal temperature to achieve high chlorination is 523 K. Oxygen is a minor impurity in the chlorine gas which appears to prevent complete chlorination from being achieved.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
NASA NTRS1992

The value of the 4-day headdown bedrest model for screening countermeasures

In order to evaluate the benefits of periodic exposure to the +G(z) vector as a countermeasure to the physiological responses to minus 6 degree head down bedrest (HDT), we considered a two-tiered approach: (a) to use 4 days HDT as a quick and inexpensive means of screening countermeasures, (b) to use a 60 day HDT to validate the most promising candidates. The approach and results of a 4 day study are described here. Methods: Nine males were admitted to our Human Research Facility for one ambulatory control day followed by 4 days HDT and were released on the next day after completion of a peak oxygen consumption test (VO(sub 2 peak)). A battery of tests was selected and standardized to evaluate the known early effects of HDT on plasma volume, early bone markers, orthostatic tolerance, physical performance, and fluid and electrolytes and their hormone regulation. Fluid sodium (Na) and potassium (K) intake and output in the urine were monitored throughout. Plasma volume was determined with a modified Evans Blue method and orthostatic tolerance with a 60 degree head-up tilt test for 30 minutes - both of which were determined on the ambulatory control day and on day 4 of HDT. Immediately after completion of the tilt test subjects were returned to the minus 6 degree position until the next morning when a VO(sub 2 peak) (horizontal ergometer) was done. This was compared to a similar control test determined on 2 separate occasions before subject admission. Results: Four hours after going HDT produced significant decreases (p less than 0.05) in the circulating concentration of fluid and electrolyte regulating hormones. Plasma volume, orthostatic tolerance and VO(sub 2 peak) changed significantly after 4 days HDT. There was also the expected natriuresis on day 1 of HDT but no significant diuresis. The consistency of the pre-bedrest VO(sub 2 peak) tilt tests and plasma volumes was remarkable. Conclusions: The 4 day HDT model seems highly promising for screening a variety of countermeasures alone and in combination before validating their benefits in extended bedrest or flight experiments.

Vernikos, J.↗
NASA NTRS2002

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.↗
DOE OSTI2019

Contaminant Cation Effect on Oxygen Transport through the Ionomers of Polymer Electrolyte Membrane Fuel Cells

We characterized the effects of cobalt (Co 2+ ) and other cation contaminants on the oxygen (O 2 ) transport properties of the PFSA ionomer used in polymer electrolyte membrane fuel cells (PEMFCs) and gained insight into the mechanisms by which contaminant cations inhibit O 2 transport. Such cations can be released by alloy catalysts and environmental conditions and pose a significant challenge to maintaining high current density performance with low platinum (Pt) loadings. We used a test cell capable of isolating the ionomer from the membrane electrode assembly (MEA), allowing for O 2 transport resistance (R O2 ) measurements using a limiting current technique. We contaminated ionomer membranes with Li + , Na + , Ni 2+ , Co 2+ , and Ce 3+ and found a general increase in R O2 for increased contamination levels and decreased water activity. In addition, our Co 2+ results indicated distinct concentration-dependent regimes. The other cation-form ionomers allowed us to separate the impacts of ion pair strength, multivalency, and reduced water uptake. We believe that these factors cause a more compressed hydrophilic domain and tortuous O 2 diffusion path, and a commensurate increase in R O2 . Lastly, we studied the impact of Co 2+ on an operating PEMFC and found an increase in R O2 consistent with the results of our isolated membrane tests.

25 ENERGY STORAGE↗
NASA NTRS2015

Comments on the MIT Assessment of the Mars One Plan

The MIT assessment of the Mars One mission plan reveals design assumptions that would cause significant difficulties. Growing crops in the crew chamber produces excessive oxygen levels. The assumed in-situ resource utilization (ISRU) equipment has too low a Technology Readiness Level (TRL). The required spare parts cause a large and increasing launch mass logistics burden. The assumed International Space Station (ISS) Environmental Control and Life Support (ECLS) technologies were developed for microgravity and therefore are not suitable for Mars gravity. Growing food requires more mass than sending food from Earth. The large number of spares is due to the relatively low reliability of ECLS and the low TRL of ISRU. The Mars One habitat design is similar to past concepts but does not incorporate current knowledge. The MIT architecture analysis tool for long-term settlements on the Martian surface includes an ECLS system simulation, an ISRU sizing model, and an analysis of required spares. The MIT tool showed the need for separate crop and crew chambers, the large spare parts logistics, that crops require more mass than Earth food, and that more spares are needed if reliability is lower. That ISRU has low TRL and ISS ECLS was designed for microgravity are well known. Interestingly, the results produced by the architecture analysis tool - separate crop chamber, large spares mass, large crop chamber mass, and low reliability requiring more spares - were also well known. A common approach to ECLS architecture analysis is to build a complex model that is intended to be all-inclusive and is hoped will help solve all design problems. Such models can struggle to replicate obvious and well-known results and are often unable to answer unanticipated new questions. A better approach would be to survey the literature for background knowledge and then directly analyze the important problems.

Mars mission↗
DOE OSTI2023

TaO x electron transport layers for CO 2 reduction Si photocathodes

Electron transport layers (ETLs) used as components of photocathodes for light-driven CO 2 reduction (CO 2 R) in aqueous media should have good electronic transport, be stable under CO 2 R conditions, and, ideally, be catalytically inert for the competing hydrogen evolution reaction (HER). Here, using planar p-Si (100) as the absorbing material, we show that TaO x satisfies all three of the above criteria. TaO x films were synthesized by both pulsed laser deposition (PLD) and radio-frequency (RF) sputtering. In both cases, careful control of the oxygen partial pressure during growth was required to produce ETLs with acceptable electron conductivity. p-Si/TaO x photocathodes were interfaced with ca. 10 nm of a CO 2 R catalyst: Cu or Au. Under front illumination with simulated AM 1.5G in CO 2 -saturated bicarbonate buffer, we observed, for both metals, faradaic efficiencies for CO 2 R products of ~50% and ~30% for PLD TaO x and RF sputtered TaO x , respectively, at photocurrent densities up to 8 mA cm -2 . p-Si/TiO 2 /Cu photocathodes were also evaluated but produced mostly H 2 (>97%) due to reduction of the TiO 2 to Ti metal under CO 2 R conditions. In contrast, a dual ETL photocathode (p-Si/TiO 2 /TaO x /Cu) was selective for CO 2 R, which suggests a strategy for separately optimizing selective charge collection and the stability of the ETL/water interface. The maximum photovoltage obtained with p-Si/TaO x /Cu devices was 300 mV which was increased to 430–460 mV by employing ion implantation to make pn + -Si/TaO x /Cu structures. Photocathodes with RF sputtered TaO x ETLs are stable for CO 2 R for at least 300 min. In conclusion, techno-economic analysis shows that the reported system, if scaled, could allow for an economically viable production of feedstocks for chemical synthesis under the adoption of specific CO 2 credit schemes, thus becoming a significant component of carbon-neutral manufacturing.

36 MATERIALS SCIENCE↗