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62 records · Page 4

Advanced rechargeable sodium batteries with novel cathodes

Various high energy density rechargeable batteries are being considered for future space applications. Of these, the sodium-sulfur battery is one of the leading candidates. The primary advantage is the high energy density (760 W h/kg theoretical). Energy densities in excess of 180 W h/kg have been realized in practical batteries. More recently, cathodes other than sulfur are being evaluated. Various new cathode materials are presently being evaluated for use in high energy density sodium batteries for advanced space applications. The approach is to carry out basic electrochemical studies of these materials in a sodium cell configuration in order to understand their fundamental behaviors. Thus far, the studies have focussed on alternative metal chlorides such as CuCl2 and organic cathode materials such as TCNE.

Di Stefano, S.↗

Lunar and Planetary Science XXXV: Weird Martian Minerals: Complex Mars Surface Processes

The session "Complex Mars Surface" included the following reports:A Reappraisal of Adsorbed Superoxide Ion as the Cause Behind the Reactivity of the Martian Soils; Sub-Surface Deposits of Hydrous Silicates or Hydrated Magnesium Sulfates as Hydrogen Reservoirs near the Martian Equator: Plausible or Not?; Thermal and Evolved Gas Analysis of Smectites: The Search for Water on Mars; Aqueous Alteration Pathways for K, Th, and U on Mars; Temperature Dependence of the Moessbauer Fraction in Mars-Analog Minerals; Acid-Sulfate Vapor Reactions with Basaltic Tephra: An Analog for Martian Surface Processes; Iron Oxide Weathering in Sulfuric Acid: Implications for Mars; P/Fe as an Aquamarker for Mars; Stable Isotope Composition of Carbonates Formed in Low-Temperature Terrestrial Environments as Martian Analogs; Can the Phosphate Sorption and Occlusion Properties Help to Elucidate the Genesis of Specular Hematite on the Mars Surface?; Sulfate Salts, Regolith Interactions, and Water Storage in Equatorial Martian Regolith; Potential Pathways to Maghemite in Mars Soils: The Key Role of Phosphate; and Mineralogy, Abundance, and Hydration State of Sulfates and Chlorides at the Mars Pathfinder Landing Site.

Source record↗

Recycling plant, human and animal wastes to plant nutrients in a closed ecological system

The essential minerals for plant growth are nitrogen, phosphorous, potassium (macronutrients), calcium, magnesium, sulfur (secondary nutrients), iron, manganese, boron, copper, zinc, chlorine, sodium, and molybdenum (micronutrients). The first step in recycling wastes will undoubtedly be oxidation of carbon and hydrogen to CO2 and H2O. Transformation of minerals to plant nutrients depends upon the mode of oxidation to define the state of the nutrients. For the purpose of illustrating the type of processing required, ash and off-gas compositions of an incineration process were assumed and subsequent processing requirements were identified. Several processing schemes are described for separating out sodium chloride from the ash, leading to reformulation of a nutrient solution which should be acceptable to plants.

Meissner, H. P.↗

Gusev-Meridiani-Type Soil Component Dissolved in Some Shock Glasses in Shergottites

Modal analysis, based on APXS, MiniTES and Mossbauer results obtained at Gusev and Meridiani sites on Mars, indicates that Martian soils consist predominantly of igneous minerals such as olivine, pyroxene and feldspar (approximately70 - 80%), with the balance consisting of alteration minerals such as sulfates, silica and chlorides]. These studies also showed that soil alteration did not occur in-situ and igneous and alteration components are derived from different sources. Below, we analyse the chemical abundance data obtained from shock glasses in shergottites using mass balance mixing models. In these models, the two main end members used are (a) host rock chemical composition and (b) the GM soils average composition as the second component. Here, we consider the S-bearing phases as indicators of added alteration phases in the shock glasses and GM soils. Although the S-bearing phase in shock glasses occurs as micron sized sulfide blebs, we showed in earlier abstracts that sulfur was originally present as sulfate in impact glass-precursor materials and was subsequently reduced to sulfide during shock melting. This conclusion is based on results obtained from S-K XANES studies, Fe/S atomic ratios in sulfide blebs and 34S/32S isotopic measurements in these sulfide blebs. Additionally, sulfur in several EET79001 Lith. A glasses is found to correlate positively with Al2O3 and CaO (and negatively with FeO and MgO), suggesting the presence of Al- and Ca- sul-fate-bearing phases. The distribution of the 87Sr/86Sr iso-topic ratios determined in Lith. A glasses (,27 &,188 and,54) indicate that Martian soil gypsum and host rock material were mixed with each other in the glass precursors. In some vugs in Lith A glass,27 detected gypsum laths. Furthermore, the Martian regolith-de-rived component (where sulfur typically occurs as sul-fate) is identified in these glasses by determining neutron produced isotopic excesses/deficits in 80Kr and 149Sm isotopes. Moreover, the suggestion that the large amount of sulfur found in,507 was sourced from pyrrhotite in the host rock, would require that excessive quantities of host rock would need to be stripped of sulfur to make this sulfide-rich glass. These results provide ample evidence that S occurred as sulfate and was added to glass precursor materials prior to impact shock.

Ross, D. K.↗

Preparation of Proton Exchange Membranes and Lithium Batteries from Melamine-containing Ormosils

Our laboratory has recently reported a series of rodcoil polymers for lithium batteries that display dimensionally stable films with good ionic conductivity. The rod segments consist of rigid linear and branched polyimides and the coil segments are polyethylene oxides (PEO). It has been proposed that good mechanical and transport properties are due to phase separation between the rod and coil segments. It was also observed that increased branching and molecular weight lead to increased conductivity. The following study was undertaken to assess the effects of phase separation in polyalkylene oxides connected by melamine linkages. Melamine was chosen as the linking unit because it provides a branching site, cation binding sites to help ionic transport between polymer chains, and the opportunity for self assembly through hydrogen bonding. Polymers were made by the reaction of cyanuric chloride with a series of amine-terminated alkylene oxides. A linear polymer was first made, followed by reaction of the third site on cyanuric chloride with varying ratios of monofunctional Jeffamine and (3-aminopropyl)triethoxysilane. The lithium trifluoromethane sulfonamide-doped polymers are then crosslinked through a sol-gel process to form free-standing films. Initial results have shown mechanically strong films with lithium conductivities on the order of 2 x 10(exp -5) S/cm at ambient temperature. In a separate study, organically modified silanes (Ormosils) that contain sulfonic acid derivatized melamines have been incorporated into proton exchange membranes. The membranes are made by reaction of the primary amine groups of various ratios of melamine derivative and difunctional Jeffamine (MW = 2000) with the epoxide group of (3-Glycidyloxypropyl)trimethoxysilane. The films were then cross-linked through a sol-gel process. Resulting sulfuric acid doped films are strong, flexible, and have proton conductivities on the order of 2 x l0(exp -2) S/cm (120 C, 25% relative humidity). Our best results have been observed when films contain 60% PEO and 40% sulfonated melamine.

Tigelaar, Dean M.↗

The role of NaCl in flame chemistry, in the deposition process, and in its reactions with protective oxides as related to hot corrosion

Sodium chloride is believed to be the primary source of turbine engine contamination that contributes to hot corrosion. The behavior of NaCl-containing aerosols ingested with turbine intake air is very complex; some of the NaCl may vaporize during combustion while some may remain as particulates. The NaCl can lead to Na2SO4 formation by several possible routes or it can contribute to corrosion directly. Hydrogen or oxygen atom reaction with NaCl(c) was shown to result in the release of Na(g). Gaseous NaCl in flames can be partially converted to gaseous Na2SO4 by homogeneous reactions. The remaining gaseous NaCl and other Na-containing molecules can act as sodium carriers for condensate deposition of Na2SO4 on cool surfaces. A frozen boundary layer theory was developed to predict the rates of deposition. The condensed phase NaCl can be converted directly to condensed Na2SO4 by reaction with sulfur oxides and O2. Reaction of gaseous NaCl with Cr2O3 results in the vapor phase transport of chromium by the formation of complex Cr-containing gaseous molecules. Similar gaseous complexes are formed with molybdenum. The presence of gaseous NaCl was shown to affect the oxidation kinetics of Ni-Cr alloys. It also causes changes in the surface morphology of Al2O3 scales formed on Al-containing alloys.

Kohl, F. J.↗

Reactions Involving Calcium and Magnesium Sulfates as Potential Sources of Sulfur Dioxide During MSL SAM Evolved Gas Analyses

The Sample Analysis at Mars (SAM) and Chemistry and Mineralogy (CheMin) instruments on the Mars Science Laboratory (MSL) have analyzed several subsamples of <150 micron fines from ten sites at Gale Crater. Three were in Yellowknife Bay: the Rocknest aeolian bedform (RN) and drilled Sheepbed mudstone from sites John Klein (JK) and Cumberland (CB). One was drilled from the Windjana (WJ) site on a sandstone of the Kimberly formation. Four were drilled from sites Confidence Hills (CH), Mojave (MJ), Telegraph Peak (TP) and Buckskin (BK) of the Murray Formation at the base of Mt. Sharp. Two were drilled from sandstones of the Stimson formation targeting relatively unaltered (Big Sky, BY) and then altered (Greenhorn, GH) material associated with a light colored fracture zone. CheMin analyses provided quantitative sample mineralogy. SAM's evolved gas analysis mass spectrometry (EGA-MS) detected H2O, CO2, O2, H2, SO2, H2S, HCl, NO, and other trace gases. This contribution will focus on evolved SO2. All samples evolved SO2 above 500 C. The shapes of the SO2 evolution traces with temperature vary between samples but most have at least two "peaks' within the wide high temperature evolution, from approx. 500-700 and approx. 700-860 C (Fig. 1). In many cases, the only sulfur minerals detected with CheMin were Ca sulfates (e.g., RN and GH), which should thermally decompose at temperatures above those obtainable by SAM (>860 C). Sulfides or Fe sulfates were detected by CheMin (e.g., CB, MJ, BK) and could contribute to the high temperature SO2 evolution, but in most cases they are not present in enough abundance to account for all of the SO2. This additional SO2 could be largely associated with x-ray amorphous material, which comprises a significant portion of all samples. It can also be attributed to trace S phases present below the CheMin detection limit, or to reactions which lower the temperatures of SO2 evolution from sulfates that are typically expected to thermally decompose at temperatures outside the SAM temperature range (e.g., Ca and Mg sulfates). Here we discuss the results of SAM-like laboratory analyses targeted at understanding this last possibility, focused on understanding if reactions of HCl or an HCl evolving phase (oxychlorine phases, chlorides, etc.) and Ca and Mg sulfates can result in SO2 evolution in the SAM temperature range.

McAdam, A. C.↗

Importance of Sulfur for Phosphorus Mobility on the Martian Surface

Sulfur and phosphorus were mobile on the martian surface, and we present evidence that sulfate was likely a control on phosphate mobility. Mobility of the two elements on the martian surface is crucial for the habitability of Mars because their availability for biochemical reactions and biological structures is a major constraint on life. In the sedimentary rocks of Gale crater, the rover Curiosity has discovered evidence of mobile S and P with the alpha particle X-ray spectrometer (APXS). Sulfur-rich fluids are evident in ubiquitous Ca-sulfate veins that crosscut the bedrock. Compelling evidence of P mobility is in nodules, veins, crusts, and haloes with P2O5 enrichments (1.5-7.5 wt%) relative to the median bedrock (0.9-1.2 wt%) and average basaltic crust (~0.9 wt%). We have investigated phosphorus mobility in Hawaiian analogues, where the primary P2O5 (0.2-2.1 wt%) is contained in Ca-apatite. Four relevant processes have emerged: (1) In open-system, circumneutral regolith weathering profiles, we found up to 40% of the P was leached over 10s-100s ka. (2) Natural acid-sulfate alteration at the Maunakea summit resulted in the dissolution of apatite and mobilization of phosphate 10s-1000s µm to rock surfaces where it formed Al-phosphates and substituted into crystalline sulfates (alunite and jarosite). (3) Experimental results indicate that basaltic sediment chemisorbs phosphate (pH < 7). (4) In experimental systems containing water, basaltic sediment, and a starting pH = 2-7, phosphate has higher solubility in chloride-rich fluids, but significantly lower solubility in sulfate-rich fluids. For example, in water doped with phosphate (~100-500 mg/L), ~60-80% of the PO43- was removed from the sulfate-rich fluid, whereas ~20% of the PO43- was removed from the Cl-rich and pure water fluids (likely via adsorption). Gypsum precipitated from the sulfate-rich fluids; the fate of phosphate in the solid residue is unconfirmed. The potential for phosphate incorporation in martian sulfates is reflected in the enrichment of P2O5 in Gale Ca-sulfate veins, based on preliminary analyses of APXS data. Models for the mobility of phosphorus in Gale crater should consider these conflicting P characteristics: (1) P solubility may have been inhibited by sulfate and (2) P¬ is enriched in diagenetic features and was therefore mobile.

Jeff A. Berger↗