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NASA NTRS2007

Use of Ionic Liquids in Rod-Coil Block Copolyimides for Improved Lithium Ion Conduction

Solvent-free, solid polymer electrolytes (SPE) have the potential to improve safety, increase design flexibility and enhance performance of rechargeable lithium batteries. Solution based electrolytes are flammable and typically incompatible with lithium metal anodes, limiting energy density. We have previously demonstrated use of polyimide rod coil block copolymers doped with lithium salts as electrolytes for lithium polymer batteries. The polyimide rod blocks provide dimensional stability while the polyethylene oxide (PEO) coil portions conduct ions. Phase separation of the rods and coils in these highly branched polymers provide channels with an order of magnitude improvement in lithium conduction over polyethylene oxide itself at room temperature. In addition, the polymers have been demonstrated in coin cells to be compatible with lithium metal. For practical use at room temperature and below, however, at least an order of magnitude improvement in ion conduction is still required. The addition of nonvolatile, room temperature ionic liquids has been shown to improve the ionic conductivity of high molecular weight PEO. Herein we describe use of these molten salts to improve ionic conductivity in the rod-coil block copolymers.

Meador, Mary Ann B.↗

NASA NTRS2007

Calcium Sulfate in Atacama Desert Basalt: A Possible Analog for Bright Material in Adirondack Basalt, Gusev Crater

The Atacama Desert in northern Chile is one of the driest deserts on Earth (< 2mm/y). The hyper-arid conditions allow extraordinary accumulations of sulfates, chlorides, and nitrates in Atacama soils. Examining salt accumulations in the Atacama may assist understanding salt accumulations on Mars. Recent work examining sulfate soils on basalt parent material observed white material in the interior vesicles of surface basalt. This is strikingly similar to the bright-white material present in veins and vesicles of the Adirondack basalt rocks at Gusev Crater which are presumed to consist of S, Cl, and/or Br. The abundance of soil gypsum/anhydrite in the area of the Atacama basalt suggested that the white material consisted of calcium sulfate (Ca-SO4) which was later confirmed by SEM/EDS analysis. This work examines the Ca-SO4 of Atacama basalt in an effort to provide insight into the possible nature of the bright material in the Adirondack basalt of Gusev Crater. The objectives of this work are to (i) discuss variations in Ca-SO4 crystal morphology in the vesicles and (ii) examine the Ca-SO4 interaction(s) with the basalt interior.

Sutter, B.↗

NASA NTRS2007

Mineralogical In-situ Investigation of Acid-Sulfate Samples from the Rio Tinto River, Spain, with a Portable XRD/XRF Instrument

A field campaign was organized in September 2006 by Centro de Astobiologica (Spain) and Washington University (St Louis, USA) for the geological study of the Rio Tinto river bed sediments using a suite of in-situ instruments comprising an ASD reflectance spectrometer, an emission spectrometer, panoramic and close-up color imaging cameras, a life detection system and NASA's CheMin 4 XRD/XRF prototype. The primary objectives of the field campaign were to study the geology of the site and test the potential of the instrument suite in an astrobiological investigation context for future Mars surface robotic missions. The results of the overall campaign will be presented elsewhere. This paper focuses on the results of the XRD/XRF instrument deployment. The specific objectives of the CheMin 4 prototype in Rio Tinto were to 1) characterize the mineralogy of efflorescent salts in their native environments; 2) analyze the mineralogy of salts and oxides from the modern environment to terraces formed earlier as part of the Rio Tinto evaporative system; and 3) map the transition from hematite-dominated terraces to the mixed goethite/salt-bearing terraces where biosignatures are best preserved.

Sarrazin, P.↗

NASA NTRS1994

Engine protection system for recoverable rocket booster

A rocket engine protection system for a recoverable rocket booster which is arranged to land in a salt water body in substantially a nose down attitude. The system includes an inflatable bag which is stowed on a portion of a flat annular rim of the aft skirt of the booster. The bag is hinged at opposing sides and is provided with springs that urge the bag open. The bag is latched in a stowed position during launch and prior to landing for recovery is unlatched to permit the bag to be urged open and into sealing engagement with the rim. A source of pressurized gas further inflates the bag and urges it into sealing engagement with the rim of the skirt where it is locked into position. The gas provides a positive pressure upon the interior of the bag to preclude entry of salt water into the skirt and into contact with the engine. A flotation arrangement may assist in precluding the skirt of the booster from becoming submerged.

Shelby, Jr., Jerry A.↗

NASA NTRS1980

Impregnated metal-polymeric functional beads

Amine containing polymeric microspheres such as polyvinyl pyridine are complexed with metal salts or acids containing metals such as gold, platinum or iron. After reduction with sodium borohydride, the salt is reduced to finely divided free metal or metal oxides, useful as catalysts. Microspheres containing covalent bonding sites can be used for labeling or separating proteins.

Rembaum, Alan↗

NASA NTRS1982

Gasifiable carbon-graphite fibers

Fine, carbon-graphite fibers do not combust during the combustion of a composite and are expelled into the air as fine conductive particles. Coating of the fibers with a salt of a metal having a work function below 4.2 eV such as an alkaline earth metal salt, e.g., calcium acetate, catalytically enhances combustion of the fibers at temperatures below 1000.degree. C. such that the fibers self-support combustion and burn to produce a non-conductive ash. Fire-polishing the fibers before application of the coating is desirable to remove sizing to expose the carbon surface to the catalyst.

Humphrey, Marshall F.↗

NASA NTRS1989

Magnetic particles

Magnetic polymer particles are formed by swelling porous, polymer particles and impregnating the particles with an aqueous solution of precursor magnetic metal salt such as an equimolar mixture of ferrous chloride and ferric chloride. On addition of a basic reagent such as dilute sodium hydroxide, the metal salts are converted to crystals of magnetite which are uniformly contained througout the pores of the polymer particle. The magnetite content can be increased and neutral buoyancy achieved by repetition of the impregnaton and neutralization steps to adjust the magnetite content to a desired level.

Chang, Manchium↗

NASA NTRS1978

Impregnated metal-polymeric functional beads

Rembaum, Alan↗

NASA NTRS2007

Mobile Element Studies in Rocks (RAT) from Columbia Hills/West Spur at Gusev

Using elemental abundances determined by SPIRIT APX spectrometer on rocks and soils at Gusev Plains and Columbia Hills/ West Spur regions, the Athena Team discussed the aqueous geochemical implications at these sites on Mars. They suggested that these rocks were exposed to variable degrees of aqueous alteration (low to high) at Gusev crater. Earlier, we developed analytical procedures for studying aqueous geochemical behavior of fluids on rocks at Meridiani. In the present study, we apply these methods to rocks at Columbia Hills/West Spur in order to understand the significance of the Gusev rock results in reference to aqueous geochemical processes on Mars . The data analysis procedure is based on treating SO3 ("a") and Cl ("b") as two variables and tracking the relationship between "a" and "b" when the fluids undergo evaporation. This process of evaporation leads to concentration changes in these two elements finally producing salt assemblages on Martian rocks. In some cases on plotting "a"/ "b" versus "b" in salt assemblages, they yield a hyperbolic distribution. The relationship is transformed into a straight line when "a"/"b" is again plotted against 1/"b" in the system. Earlier, we used this procedure in the case of Merdiani rock abrasion tool (RAT) rocks and in this study, we discuss the application of this procedure to Gusev rocks. This study shows that the Gusev Plains rocks were exposed to low SO3/Cl solutions (sulfate-poor) for short period of time (weak interaction), whereas solutions with high SO3/Cl ratios (sulfate-rich) seem to have pervasively interacted with Columbia Hills/ West Spur rocks (strong interaction) at Gusev crater. Our conclusions seem to be consistent with the Mossbauer results given for these rocks

Rao, M. N.↗

NASA NTRS2007

Dust Modeling with GEOS-Chem: Evidence for Acidic Uptake on Dust Surfaces during INTEX-B

We use measurements of aerosol ion composition and size made from the DC8 aircraft during the 2006 INTEX-B airborne campaign to identify mineral dust signatures, and look for evidence for interaction of dust with acidic components. Coating of dust with sulfate or nitrate favors the role of dust particles as cloud condensation nucleii, can promote further uptake of SO2 and N2O5, can impact NOx/HNO3 partitioning, and can shift sulfate or nitrate towards larger sizes, affecting atmospheric lifetimes for both aerosol and gas components. Mineral dust had a pervasive presence on flights made during the Northern Pacific deployment of the INTEX-B mission. We use scatter plots of ion mixing ratios with Na+ and Ca(2+) to distinguish sea salt and mineral components of the aerosol distribution, respectively. Positive correlations of non-sea-salt sulfate and nitrate with calcium indicate that the dusty air stream is associated with polluted air masses. Sulfate-ammonium scatter plots indicate sulfate to be primarily in the form of (NH4)2SO4. A positive correlation between Ca(2+) and NO-, but little evidence of NH4NO3, suggests that NO3- may be associated with mineral dust surfaces. 3-d model simulations conducted with the GEOS-Chem chemical transport model indicate that transpacific transport from East Asia was principally responsible for the dust observed from the aircraft over the Pacific. We compare the aerosol component relationships in the model with those observed. Uptake of sulfate and nitrate on the dust is not yet represented in the model.

Fairlie, T. Duncan↗

NASA NTRS2005

The Rio Tinto Basin, Spain: Mineralogy, Sedimentary Geobiology, and Implications for Interpretation of Outcrop Rocks at Meridiani Planum, Mars

Exploration by the NASA rover Opportunity has revealed sulfate- and hematite-rich sedimentary rocks exposed in craters and other surface features of Meridiani Planum, Mars. Modern, Holocene, and Plio-Pleistocene deposits of the Rio Tinto, southwestern Spain, provide at least a partial environmental analog to Meridiani Planum rocks, facilitating our understanding of Meridiani mineral precipitation and diagenesis, while informing considerations of martian astrobiology. Oxidation, thought to be biologically mediated, of pyritic ore bodies by groundwaters in the source area of the Rio Tinto generates headwaters enriched in sulfuric acid and ferric iron. Seasonal evaporation of river water drives precipitation of hydronium jarosite and schwertmannite, while (Mg,Al,Fe(sup 3+))-copiapite, coquimbite, gypsum, and other sulfate minerals precipitate nearby as efflorescences where locally variable source waters are brought to the surface by capillary action. During the wet season, hydrolysis of sulfate salts results in the precipitation of nanophase goethite. Holocene and Plio-Pleistocene terraces show increasing goethite crystallinity and then replacement of goethite with hematite through time. Hematite in Meridiani spherules also formed during diagenesis, although whether these replaced precursor goethite or precipitated directly from groundwaters is not known. The retention of jarosite and other soluble sulfate salts suggests that water limited the diagenesis of Meridiani rocks. Diverse prokaryotic and eukaryotic microorganisms inhabit acidic and seasonally dry Rio Tinto environments. Organic matter does not persist in Rio Tinto sediments, but biosignatures imparted to sedimentary rocks as macroscopic textures of coated microbial streamers, surface blisters formed by biogenic gas, and microfossils preserved as casts and molds in iron oxides help to shape strategies for astrobiological investigation of Meridiani outcrops.

Fernandez-Remolar, David C.↗

NASA NTRS2008

Global Radiative Forcing of Coupled Tropospheric Ozone and Aerosols in a Unified General Circulation Model

Global simulations of sea salt and mineral dust aerosols are integrated into a previously developed unified general circulation model (GCM), the Goddard Institute for Space Studies (GISS) GCM II', that simulates coupled tropospheric ozone-NOx-hydrocarbon chemistry and sulfate, nitrate, ammonium, black carbon, primary organic carbon, and secondary organic carbon aerosols. The fully coupled gas-aerosol unified GCM allows one to evaluate the extent to which global burdens, radiative forcing, and eventually climate feedbacks of ozone and aerosols are influenced by gas-aerosol chemical interactions. Estimated present-day global burdens of sea salt and mineral dust are 6.93 and 18.1 Tg with lifetimes of 0.4 and 3.9 days, respectively. The GCM is applied to estimate current top of atmosphere (TOA) and surface radiative forcing by tropospheric ozone and all natural and anthropogenic aerosol components. The global annual mean value of the radiative forcing by tropospheric ozone is estimated to be +0.53 W m(sup -2) at TOA and +0.07 W m(sup -2) at the Earth's surface. Global, annual average TOA and surface radiative forcing by all aerosols are estimated as -0.72 and -4.04 W m(sup -2), respectively. While the predicted highest aerosol cooling and heating at TOA are -10 and +12 W m(sup -2) respectively, surface forcing can reach values as high as -30 W m(sup -2), mainly caused by the absorption by black carbon, mineral dust, and OC. We also estimate the effects of chemistry-aerosol coupling on forcing estimates based on currently available understanding of heterogeneous reactions on aerosols. Through altering the burdens of sulfate, nitrate, and ozone, heterogeneous reactions are predicted to change the global mean TOA forcing of aerosols by 17% and influence global mean TOA forcing of tropospheric ozone by 15%.

Liao, Hong↗

NASA NTRS2005

Global Impacts of Gas-Phase Chemistry-Aerosol Interactions on Direct Radiative Forcing by Anthropogenic Aerosols and Ozone

We present here a first global modeling study on the influence of gas-phase chemistry/aerosol interactions on estimates of anthropogenic forcing by tropospheric O3 and aerosols. Concentrations of gas-phase species and sulfate, nitrate, ammonium, black carbon, primary organic carbon, secondary organic carbon, sea salt, and mineral dust aerosols in the preindustrial, present-day, and year 2100 (IPCC SRES A2) atmospheres are simulated online in the Goddard Institute for Space Studies general circulation model II' (GISS GCM II'). With fully coupled chemistry and aerosols, the preindustrial, presentday, and year 2100 global burdens of tropospheric ozone are predicted to be 190, 319, and 519 Tg, respectively. The burdens of sulfate, nitrate, black carbon, and organic carbon are predicted respectively to be 0.32. 0.18, 0.01, 0.33 Tg in preindustrial time, 1.40, 0.48, 0.23, 1.60 Tg in presentday, and 1.37, 1.97, 0.54, 3.31 Tg in year 2100. Anthropogenic O3 is predicted to have a globally and annually averaged present-day forcing of +0.22 W m(sup -2) and year 2100 forcing of +0.57 W m(sup -2) at the top of the atmosphere (TOA). Net anthropogenic TOA forcing by internally mixed sulfate, nitrate, organic carbon, and black carbon aerosols is estimated to be virtually zero in the present-day and +0.34 W m(sup -2) in year 2100, whereas it is predicted to be -0.39 W m(sup -2) in present-day and -0.61 W m(sup -2) in year 2100 if the aerosols are externally mixed. Heterogeneous reactions are shown to be important in affecting anthropogenic forcing. When reactions of N2O5, NO3, NO2, and HO2 on aerosols are accounted for, TOA anthropogenic O3 forcing is less by 20-45% in present-day and by 20-32% in year 2100 at mid to high latitudes in the Northern Hemisphere, as compared with values predicted in the absence of heterogeneous gas aerosol reactions. Mineral dust uptake of HNO3 and O3 is shown to have practically no influence on anthropogenic O3 forcing. Heterogeneous reactions of N2Os, NO3, NO2, and HO2 are predicted to have noticeable impacts on anthropogenic aerosol forcing over industrialized areas, leading to 0-2 W m(sup -2) more anthropogenic aerosol cooling in present-day and 2-8 W m(sup -2) more cooling in year 2100 in these areas as compared with forcings calculated in the absence of heterogeneous reactions. Sea salt uptake of SO2 reduces the magnitude of TOA aerosol cooling by 0.5-1 W m(sup -2) over the oceans around 60 N in the present-day and year 2100 scenarios. Near dust sources, mineral dust uptake of SO2 and HNO3 leads to less anthropogenic aerosol cooling by 0.5-1 W m(sup -2) in the present day and 1-2 W m(sup -2) in year 2100.

Liao, Hong↗

NASA NTRS2008

Solid-State High-Temperature Power Cells

All-solid-state electrochemical power cells have been fabricated and tested in a continuing effort to develop batteries for instruments for use in environments as hot as 500 C. Batteries of this type are needed for exploration of Venus, and could be used on Earth for such applications as measuring physical and chemical conditions in geothermal and oil wells, processing furnaces, and combustion engines. In the state-of-the-art predecessors of the present solid-state power cells, fully packaged molten eutectic salts are used as electrolytes. The molten-salt-based cells can be susceptible to significant amounts of self-discharge and corrosion when used for extended times at elevated temperatures. In contrast, all-solid-state cells such as the present ones are expected to be capable of operating for many days at temperatures up to 500 C, without significant self-discharge. The solid-state cell described here includes a cathode made of FeS2, an electrolyte consisting of a crystalline solid solution of equimolar amounts of Li3PO4 and Li4SiO4, and an anode made of an alloy of Li and Si (see figure). The starting material for making the solid electrolyte is a stoichiometric mixture of Li3PO4, SiO2, and Li3CO2. This mixture is ball-milled, then calcined for two hours at a temperature of 1,100 C, then placed in a die atop the cathode material. Next, the layers in the die are squeezed together at a pressure between 60 and 120 MPa for one hour at a temperature of 600 C to form a unitary structure comprising the solid electrolyte and cathode bonded together. Finally, the lithium-alloy anode is pressure-bonded to the solid electrolyte layer, using an intermediate layer of pure lithium. In one test of a cell of this type, a discharge rate of about 1 mA per gram of cathode material was sustained for 72 hours at a temperature of about 460 C. This is about three times the discharge rate required to support some of the longer duration Venus-exploration mission scenarios.

Whitacre, Jay↗

NASA NTRS2009

Fluid-Evaporation Records Preserved in Meridiani Rocks

We have shown earlier that the high SO3/Cl ratios found in secondary mineral assemblages in shergottite GRIM glasses (Gas-Rich Impact-Melt) likely resulted from interactions of regolith materials with sulfate-rich (and Cl-poor) solutions. The low SO3/Cl ratios determined in secondary salts in nakhalite fracture-fillings presumably formed by rock interactions with chloride-rich (and SO4-poor) solutions near Mars surface. The SO3 and Cl abundances determined by APXS in abraded rocks (RAT) from Endurance, Fram and Eagle craters indicate that these salt assemblages likely formed by evaporative concentration of brine fluids at Meridiani. The SO3/Cl ratios in the abraded rocks are examined here, instead of their absolute abundances, because the abundance ratios might provide better guide-lines for tracking the evolution of evaporating fluids at Meridiani. The SO3/Cl ratios in these samples, in turn, might provide clues for the mobile element ratios of the altering fluids that infiltrated into the Meridiani rocks.

Rao, M. N.↗

NASA NTRS2009

Effect of Pharmacologically-Induced Hypovolemia on Aerobic Capacity

Decreased peak oxygen consumption (VO2pk) and an elevated exercise heart rate (HR) response are associated with a reduction in plasma volume (PV) after space flight and bed rest, a space flight analog. Reduced VO2pk and submaximal exercise tolerance would negatively impact an astronaut s ability to perform near maximal work that would be required in the event of an emergency. We previously have administered IV furosemide followed by a low salt diet to model PV loss and orthostatic intolerance observed after spaceflight. Purpose: To determine whether a pharmacologically-induced reduction in PV results in decreased VO2pk and elevated exercise HR response. Methods: Six subjects (5M, 1F) performed two graded peak cycle tests (work rate increased by 35 or 50 W every 3 min), once while normovolemic and once while hypovolemic. HR and expired respiratory gases were continuously measured. To induce hypovolemia, subjects were administered a single dose of IV furosemide (0.5 mg.kg-1) 30 hr before exercise testing and then consumed a low-salt diet (10 mEq.d(sup -1)). PV was measured using carbon monoxide rebreathing. Exercise HR and VO2 responses were quantified as the area under the curve (AUC) calculated over each quartile of the peak test, based on test time in the hypovolemia condition. Paired t-tests were used to test for differences in PV, VO2pk, and peak HR between conditions. Repeated-measures ANOVAs were used to test for differences in AUC between conditions. Results: PV (3.32+/-0.12 vs. 2.77+/-0.16 L, p<0.05) and VO2pk (3.30+/-0.67 vs. 2.90+/-0.57 L.min(sup -1), p<0.05) were lower during hypovolemia than during normovolemia, but peak HR was not different (187+/-5 vs. 187+/-5 bpm). The AUC for VO2 and HR was different (p<0.05) between conditions only in the highest quartile: HR was 4% higher and VO2 was 5% lower during the hypovolemia condition. Conclusion: The mean difference in VO2pk (-12%) between normovolemia and hypovolemia was similar to the mean difference in PV (-17%). Similar decreases in PV and VO2pk have been observed following short duration space flight, suggesting that pharmacologically-induced PV loss can be used to model microgravity-induced reductions in VO2pk.

Everett, Meghan E.↗

NASA NTRS2007

Lithium Dinitramide as an Additive in Lithium Power Cells

Lithium dinitramide, LiN(NO2)2 has shown promise as an additive to nonaqueous electrolytes in rechargeable and non-rechargeable lithium-ion-based electrochemical power cells. Such non-aqueous electrolytes consist of lithium salts dissolved in mixtures of organic ethers, esters, carbonates, or acetals. The benefits of adding lithium dinitramide (which is also a lithium salt) include lower irreversible loss of capacity on the first charge/discharge cycle, higher cycle life, lower self-discharge, greater flexibility in selection of electrolyte solvents, and greater charge capacity. The need for a suitable electrolyte additive arises as follows: The metallic lithium in the anode of a lithium-ion-based power cell is so highly reactive that in addition to the desired main electrochemical reaction, it engages in side reactions that cause formation of resistive films and dendrites, which degrade performance as quantified in terms of charge capacity, cycle life, shelf life, first-cycle irreversible capacity loss, specific power, and specific energy. The incidence of side reactions can be reduced through the formation of a solid-electrolyte interface (SEI) a thin film that prevents direct contact between the lithium anode material and the electrolyte. Ideally, an SEI should chemically protect the anode and the electrolyte from each other while exhibiting high conductivity for lithium ions and little or no conductivity for electrons. A suitable additive can act as an SEI promoter. Heretofore, most SEI promotion was thought to derive from organic molecules in electrolyte solutions. In contrast, lithium dinitramide is inorganic. Dinitramide compounds are known as oxidizers in rocket-fuel chemistry and until now, were not known as SEI promoters in battery chemistry. Although the exact reason for the improvement afforded by the addition of lithium dinitramide is not clear, it has been hypothesized that lithium dinitramide competes with other electrolyte constituents to react with lithium on the surface of the anode to form a beneficial SEI. Apparently, nitrides and oxides that result from reduction of lithium dinitramide on the anode produce a thin, robust SEI different from the SEIs formed from organic SEI promoters. The SEI formed from lithium dinitramide is more electronically insulating than is the film formed in the presence of an otherwise identical electrolyte that does not include lithium dinitramide. SEI promotion with lithium dinitramide is useful in batteries with metallic lithium and lithium alloy anodes.

Gorkovenko, Alexander A.↗

NASA NTRS2010

Contaminated water treatment

Method and system for processing of a liquid ("contaminant liquid") containing water and containing urine and/or other contaminants in a two step process. Urine, or a contaminated liquid similar to and/or containing urine and thus having a relatively high salt and urea content is passed through an activated carbon filter to provide a resulting liquid, to remove most of the organic molecules. The resulting liquid is passed through a semipermeable membrane from a membrane first side to a membrane second side, where a fortified drink having a lower water concentration (higher osmotic potential) than the resulting liquid is positioned. Osmotic pressure differential causes the water, but not most of the remaining inorganic (salts) contaminant(s) to pass through the membrane to the fortified drink. Optionally, the resulting liquid is allowed to precipitate additional organic molecules before passage through the membrane.

Gormly, Sherwin J.↗