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Viewgraphs of the sodium sulfur program are presented. Sodium sulfur low earth orbit (LEO) cells are described. Topics covered include cell sizes, areas of improvement, and NaS cell testing. Sodium sulfur cell and battery designs continue to evolve with significant improvement demonstrated in resistance, rechargeability, cycle life, energy density, and electrolyte characterization.
Chromic acid has long been used to produce a thin, corrosion resistant (Type I) coating on aluminum. Following anodizing, the hardware was sealed using a sodium dichromate solution. Sealing closes up pores inherent in the anodized coating, thus improving corrosion resistance. The thinness of the brittle coating is desirable from a fatigue standpoint, and chromium was absorbed by the coating during the sealing process, further improving corrosion resistance. Unfortunately, both chromic acid and sodium dichromate contain carcinogenic hexavalent chromium. Sulfuric acid is being considered as a replacement for chromic acid. Sulfuric acid of 10-20 percent concentration has traditionally been used to produce relatively thick (Types II and III) or abrasion resistant (Type III) coatings. A more dilute, that is five weight percent, sulfuric acid anodizing process, which produces a thinner coating than Type II or III, with nickel acetate as the sealant has been developed. The process was evaluated in regard to corrosion resistance, throwing power, fatigue life, and processing variable sensitivity, and shows promise as a replacement for the chromic acid process.
Intramolecular carbon, hydrogen, and sulfur isotope ratios were measured on a homologous series of organic sulfonic acids discovered in the Murchison meteorite. Mass-independent sulfur isotope fractionations were observed along with high deuterium/hydrogen ratios. The deuterium enrichments indicate formation of the hydrocarbon portion of these compounds in a low-temperature environment that is consistent with that of interstellar clouds. Sulfur-33 enrichments observed in methanesulfonic acid could have resulted from gas-phase ultraviolet irradiation of a precursor, carbon disulfide. The source of the sulfonic acid precursors may have been the reactive interstellar molecule carbon monosulfide.
Destructive physical analysis (DPA) was used to study the effects of microgravity on the sulfur electrode in sodium-sulfur cells. The cells examined in this work were provided by the Air Force Research Laboratory (AFRL) from their program on sodium-sulfur technology. The Naval Research Laboratory (NRL) provided electrical characterization of the flight-tested and ground-tested cells.
Heterogeneous chemistry of nitrous acid (HONO) on liquid sulfuric acid (H2SO4) Was investigated at conditions that prevail in the stratosphere. The measured uptake coefficient (gamma) of HONO on H2SO4 increased with increasing acid content, ranging from 0.03 for 65 wt % to about 0.1 for 74 wt %. In the aqueous phase, HONO underwent irreversible reaction with H2SO4 to form nitrosylsulfuric acid (NO(+)HSO4(-). At temperatures below 230 K, NO(+)HSO4(-) was observed to be stable and accumulated in concentrated solutions (less than 70 wt % H2SO4) but was unstable and quickly regenerated HONO in dilute solutions (less than 70 wt %). HCl reacted with HONO dissolved in sulfuric acid, releasing gaseous nitrosyl chloride (ClNO). The reaction probability between HCl and HONO varied from 0.01 to 0.02 for 60-72 wt % H2SO4. In the stratosphere, ClNO photodissociates rapidly to yield atomic chlorine, which catalytically destroys ozone. Analysis of the laboratory data reveals that the reaction of HCl with HONO on sulfate aerosols can affect stratospheric ozone balance during elevated sulfuric acid loadings after volcanic eruptions or due to emissions from the projected high-speed civil transport (HSCT). The present results may have important implications on the assessment of environmental acceptability of HSCT.
The 1200 C oxidation behavior of NiAl was examined at various levels of sulfur and zirconium dopants to test the possibility of a critical S/Zr ratio required for adhesion. Cyclic furnace testing for 200 1 -hr cycles and interrupted testing for 500 hr were used as screening tests. Pure NiAl and NiAl(Zr) with 0. 14 at.% Zr were chosen as model base compositions; they exhibited normal, slow-growing scales (3 Mg/sq cm) with excellent adhesion for the Zr-doped alloys. NiAl with about 120 ppma S exhibited a substantial weight loss (-20 Mg/sq cm) in cyclic tests and a very large weight gain (+60 Mg/sq cm) in interrupted tests. The major surface phase remained as alpha -Al2O3. Sulfur doping the NiAl(Zr) alloy caused massive weight gains of 80 - 100 Mg/sq cm, swelling, cracking, and nearly complete conversion into NiAl2O4, and alpha- Al2O3. The initial objective of determining critical S/Zr ratios for adhesion was therefore unattainable. Initiation of the catastrophic attack was examined after a 10 hr exposure, revealing a few sites of broad, raised, and cracked ridges. In cross-section, the ridges appeared as modular intrusions, with a complex, fractal, oxide-metal interface. They were primarily alumina (with occasional entrapped islands of NiAl2O4 or pure Ni metal). They possessed a unique microstructure consisting of 0.3 microns lamellae, separated by 0.1 microns open channels. This allowed for rapid growth controlled by gaseous diffusion. The microstructure is discussed in terms of SO2 evolution and a sulfur-driven de-passivation process.
The Total Ozone Mapping Spectrometer (TOMS) instruments are spatially-scanning UV spectrometers that have produced daily global images of total ozone over the last 21 years since the launch of the Nimbus 7 satellite. The instruments use a total ozone retrieval algorithm pioneered by J.V. Dave and C. L. Mateer for the Nimbus 4 Backscatter Ultraviolet (BUV) instrument, designed by D.F. Heath. The TOMS ozone maps have revealed the relations between total ozone and atmospheric dynamics, and shown the dramatic losses of ozone in the Antarctic ozone hole and the Northern hemisphere. The accepted long-term trends in global, regional, and local ozone are derived from data from the Nimbus 7 TOMS and three successive TOMS flights on Russian, Japanese, and American satellites. The next TOMS flight will be launched in 2000. The contiguous mapping design and fortuitous choice of TOMS wavelengths bands also permitted imaging of a second atmospheric gas, sulfur dioxide, which is transient due to its short lifetime. The importance of this measurement was first realized after the eruption of El Chichon volcano in 1982. The extreme range of sizes of volcanic eruptions and the 'associated danger require observations from a distant observing platform. The first quantitative time series of the input of sulfur dioxide by explosive volcanic eruptions into the atmosphere thus was developed from the TOMS missions. Finally, the Rayleigh and aerosol scattering spectral characteristic and reflectivity complete the four dominant pieces of information in the near UV albedo of the Earth. The four parameters are derived with a linear algorithm, the absorption coefficients of the gases, and effective paths computed from radiative transfer tables. Absorbing aerosol clouds (smoke, dust, volcanic ash) are readily identified by their deviation from a Rayleigh signature. The greatest shortcoming of the TOMS dataset is the 24 hour time resolution that is produced by the polar orbit of the satellite. Dynamic phenomena, such as upper air fronts that modulate total ozone and volcanic eruptions of sulfur dioxide and ash, cannot be adequately resolved. It is hoped that UV observations from geostationary satellites will soon be made to test the value of this unique information in weather forecasting and aviation safety.
The Total Ozone Mapping Spectrometer (TOMS) instruments are spatially-scanning UV spectrometers that have produced daily global images of total ozone over the last 21 years since the launch of the Nimbus 7 satellite. The instruments use a total ozone retrieval algorithm pioneered by J.V. Dave and C. L. Mateer for the Nimbus 4 Backscatter Ultraviolet (BUV) instrument, designed by D.F. Heath. The TOMS ozone maps have revealed the relations between total ozone and atmospheric dynamics, and shown the dramatic losses of ozone in the Antarctic ozone hole and the Northern hemisphere. The accepted long-term trends in global, regional, and local ozone are derived from data from the Nimbus 7 TOMS and three successive TOMS flights on Russian, Japanese, and American satellites. The next TOMS flight will be launched in 2000. The contiguous mapping design and fortuitous choice of TOMS wavelengths bands also permitted imaging of a second atmospheric gas, sulfur dioxide, which is transient due to its short lifetime. The importance of this measurement was first realized after the eruption of El Chichon volcano in 1982. The extreme range of sizes of volcanic eruptions and the associated danger require observations from a distant observing platform. The first quantitative time series of the input of sulfur dioxide by explosive volcanic eruptions into the atmosphere thus was developed from the TOMS missions. Finally, the Rayleigh and aerosol scattering spectral characteristic and reflectivity complete the four dominant pieces of information in the near UV albedo of the Earth. The four parameters are derived with a linear algorithm, the absorption coefficients of the gases, and effective paths computed from radiative transfer tables. Absorbing aerosol clouds (smoke, dust, volcanic ash) are readily identified by their deviation from a Rayleigh signature. The greatest shortcoming of the TOMS dataset is the 24 hour time resolution that is produced by the polar orbit of the satellite. Dynamic phenomena, such as upper air fronts that modulate total ozone and volcanic eruptions of sulfur dioxide and ash, cannot be adequately resolved. It is hoped that UV observations from geostationary satellites will soon be made to test the value of this unique information in weather forecasting and aviation safety.
Sensitive, high resolution measurements of S-32, S-31, and S-34 in individual pyrite grains in martian meteorite ALH84001 by an in situ ion microprobe multi-collection technique reveal mass-independent anomalies in Delta.S-33 (Delta.S-33 = delta.S-33 - 0.516delta.S-34) in addition to the lowest 634S found in an extraterrestrial material. Low delta.S-34 values in two pyrite grains intimately associated with carbonate in ALH84001 can be explained by the sensitivity of sulfur to fractionations in the geologic environment. Anomalies in Delta.S-33 recorded in ALH84001 pyrites probably formed by gas-phase reactions in the early martian atmosphere (>4 Ga). The discovery of clearly resolvable Delta-S33 anomalies in 2 of 12 ALH84001 pyrites analyzed in their petrographic context in thin section, is considered strong evidence for crust-atmosphere exchange and the global cycling of volatile sulfur species on early Mars. These results corroborate previous measurements by Farquhar and co-workers who used a different technique that measures that bulk Delta.S-33 values of martian meteorites. These independent techniques, and their results, suggest that sulfur affected by mass-independent fractionation is common on Mars.
Second-order spallation phenomena have been noted for Y-doped Rene'N5 after long term oxidation at 1150 degrees C. The reason for this behavior has not been conclusively identified. A mass equivalence analysis has shown that the surface recession resulting from oxidation has the potential of releasing about 0.15 monolayer of sulfur for every 1 mg/sq cm of oxygen reacted for an alloy containing 5 ppmw of sulfur. This amount is significant in comparison to levels that have been shown to result in first-order spallation behavior for undoped alloys. Oxidative recession is therefore speculated to be a contributing source of sulfur and second-order spallation for Y-doped alloys.
A combination of CN counts, Ames wire impactor size analyses and optical particle counter data in aircraft exhaust results in a continuous particle size distribution between 0.01 micrometer and 1 micrometer particle radius sampled in the exhaust of a Boeing 757 research aircraft. The two orders of magnitude size range covered by the measurements correspond to 6-7 orders of magnitude particle concentration. CN counts and small particle wire impactor data determine a nucleation mode, composed of aircraft-emitted sulfuric acid aerosol, that contributes between 62% and 85% to the total aerosol surface area and between 31% and 34% to its volume. Soot aerosol comprises 0.5% of the surface area of the sulfuric acid aerosol. Emission indices are: EIH2SO4 = 0.05 g/kgFUEL and (0.2-0.5) g/kgFUEL (for 75 ppmm and 675 ppmm fuel-S, respectively), 2.5E4<EISOOT<1.3E-3 g/kgFUEL, and EICN 8E14 and 1.3E16 particles/kgFUEL (for 75 and 675 ppmm fuel-S). The sulfur (gas) to H2SO4 (particle) conversion efficiency is between 10% and 25%.
A new hyperthermophilic, anaerobic, sulfur-reducing, organo-heterotrophic archaeon, strain OGL-20P, was isolated from "black smoker" chimney material at the Rainbow hydrothermal vent site in the Atlantic Ocean (36.2 N; 33.9 W). The cells of strain OGL-20P have irregular coccoid shape and are motile with a single flagellum. Growth occurs within pH range of 5.5-8.2 (optimal at pH 7.0-7.2), salinity range of 1-5% NaCl (optimal concentration 3% NaCl wt/vol), and temperature range of +55 C to +94 C (optimal growth at +83 C to +85 C). Strain OGL-20P is resistant to freezing (at -20 C). New isolate is strictly anaerobic with sulfur-type of respiration. A limited number of compounds are utilized as electron donors, including peptone, becto-tryptone, casamino-acids, and yeast extract but does not grow with separate amino acids. Sulfur and Iron can be used as electron acceptors; but not sulfate, sulfite, thiosulfate or nitrate. Strain OGL-20P is resistant to chloramphenicol, kanamycin, and gentamycin. Growth of str. OGL20P is inhibited by tetracyclin but not by Na2MoO4. The G+C content of DNA is 57.2 mol%. The 16S ribosomal RNA sequence analysis allows one to classify strain OGL-20P as a representative of a now species of Thermococcus genus. The name Thermococcus sulfurophilus op. nov., was suggested for the new isolate, type strain OGL-20P (sup T) (= ATCC BAA_394 (sup T) = DSM...(supT)).
To assess the role of oxygenated volatile organic compounds in the upper troposphere and lower stratosphere, the interactions of a series of small organic compounds with low-temperature aqueous sulfuric acid will be evaluated. The total amount of organic material which may be taken up from the gas phase by dissolution, surface layer formation, and reaction during the particle lifetime will be quantified. Our current results for acetaldehyde uptake on 40 - 80 wt% sulfuric acid solutions will be compared to those of methanol, formaldehyde, and acetone to investigate the relationships between chemical functionality and heterogeneous activity. Where possible, equilibrium uptake will be ascribed to component pathways (hydration, protonation, etc.) to facilitate evaluation of other species not yet studied in low temperature aqueous sulfuric acid.
Galileo's Near Infrared Mapping Spectrometer (NIMS) detected hydrogen peroxide, carbon dioxide and a hydrated material on Europa's surface, the latter interpreted as hydrated sulfuric acid (H2SO4*nH2O) or hydrated salts. Related compounds are molecular oxygen, sulfur dioxide, and two chromophores, one that is dark in the ultraviolet(UV) and concentrated on the trailing side, the other brighter in the UV and preferentially distributed in the leading hemisphere. The UV-dark material has been suggested to be sulfur.
Chondrules probably formed by melting and subsequent cooling of solid precursors. Evaporation during chondrule melting may have resulted in depletion of volatile elements in chondrules. It is known that kinetic evaporation, especially evaporation from a melt, often leads to enrichment of heavy isotopes in an evaporation residue. However, no evidence for a large degree of heavy-isotope enrichment has been reported in chondrules for K, Mg, Si, and Fe (as FeO). The lack of isotopic fractionation has also been found for sulfur in troilites (FeS) within Bishunpur (LL3.1) and Semarkona (LL3.0) chondrules by an ion microprobe study. The largest fractionation, found in only one grain, was 2.7 +/- 1.4 %/amu, while all other troilite grains showed isotopic fractionations of <1 %/amu. The suppressed isotopic fractionation has been interpreted as results of (i) rapid heating of precursors at temperatures below the silicate solidus and (ii) diffusion-controlled evaporation through a surrounding silicate melt at temperatures above the silicate solidus. The kinetic evaporation model suggests that a rapid heating rate of >10(exp 4)-10(exp 6) K/h for a temperature range of 1000-1300 C is required to explain observed isotopic fractionations. Such a rapid heating rate seems to be difficult to be achieved in the X-wind model, but can be achieved in shock wave heating models. In this study, we have applied the sulfur evaporation model to the shock wave heating conditions of to evaluate evaporation of sulfur and accompanying isotopic fractionation during shock wave heating at temperatures below the silicate solidus.
Hypobromous acid (HOBr) is a key species linking inorganic bromine to the chlorine and odd hydrogen chemical families. We have measured the solubility of HOBr in 45 - 70 wt% sulfuric acid solutions representative of upper tropospheric and lower stratospheric aerosol composition. Over the temperature range 201 - 252 K, HOBr is quite soluble in sulfuric acid, with an effective Henry's law coefficient, H* = 10(exp 4) - 10(exp 7) mol/L/atm. H* is inversely dependent on temperature, with Delta H = -46.2 kJ/mol and Delta S = -106.2 J/mol/K for 55 - 70 wt% H2SO4 solutions. Our study includes temperatures which overlap both previous measurements of HOBr solubility. For uptake into aqueous 45 wt% H2SO4, the solubility can be described by log H* = 3665/T - 10.63. For 55 - 70 wt% H2SO4, log H* = 2412/T - 5.55. At temperatures colder than approx. 213 K, the solubility of HOBr in 45 wt% H2SO4 is noticeably larger than in 70 wt% H2SO4. The solubility of HOBr is comparable to that of HBr, indicating that upper tropospheric and lower stratospheric aerosols should contain equilibrium concentrations of HOBr which equal or exceed those of HBr. Our measurements indicate chemical reaction of HOBr upon uptake into aqueous sulfuric acid in the presence of other brominated gases followed by evolution of gaseous products including Br2O and Br2, particularly at 70 wt% H2SO4.
NASA's 2003 Mars Exploration Rover (MER) missions, Spirit and Opportunity, have been performing exciting surface exploration studies for the past six months. These two robotic missions were aimed at examining the presence of water and, thus, any evidence of life, and at understanding the geological conditions of Mars, These rovers have been successfully assisted by primary lithium-sulfur dioxide batteries during the critical entry, descent, and landing (EDL) maneuvers. These batteries were located on the petals of the lander, which, unlike in the Mars Pathfinder mission, was designed only to carry the rover. The selection of the lithium-sulfur dioxide battery system for this application was based on its high specific energy and high rate discharge capability, combined with low heat evolution, as dictated by this application. Lithium-sulfur dioxide batteries exhibit voltage delay, which tends to increase at low discharge temperatures, especially after extended storage at warm temperatures, In the absence of a depassivation circuit, as provided on earlier missions, e.g., Galileo, we were required to depassivate the lander primary batteries in a unique manner. The batteries were brought onto a shunt-regulated bus set at pre-selected discharge voltages, thus affecting depassivation during constant discharge voltages. Several ground tests were preformed, on cells, cell strings and battery assembly with five parallel strings, to identify optimum shunt voltages and durations of depassivation. We also examined the repassivation of lithium anodes, subsequent to depassivation. In this paper, we will describe these studies, in detail, as well as the depassivation of the lander flight batteries on both Spirit and Opportunity rover prior to the EDL sequence and their performance during landing on Mars.
A hyperthermophilic, sulfur-reducing, organo-heterotrophic archaeon, strain OGL-20P was isolated from black smoker chimney material from the Rainbow hydrothermal vent site on the Mid-Atlantic Ridge (36.2 N, 33.9 W). The cells of strain OGL-20P(sup T) have an irregular coccoid shape and are motile with a single flagellum. Growth was observed within the pH range 5.0-8.5 (optimum pH 7.0), NaCl concentration range 1-5 % (w/v) (optimum 3%), and temperature range 55-94 C (optimum 83-85 C). The novel isolate is strictly anaerobic and obligately dependent upon elemental sulfur as an electron acceptor, but it does not reduce sulfate, sulfite, thiosulfate, iron (III) or nitrate. Proteolysis products (peptone, bacto-tryptone, casamino-acids, and yeast extract) are utilized as substrates during sulfur-reduction. Strain OGL-20P(sup T) is resistant to ampicillin, chloramphenicol, kanamycin, and gentamycin, but sensitive to tetracycline and rifampicin. The G+C content of DNA is 52.9 mol%. The 16S rRNA gene sequence analysis revealed that strain OGL-20P(sup T) is closely related to Thermococcus coalescens and related species, but no significant homology by DNA-DNA hybridization was observed between those species and the new isolate. On the basis of physiological and molecular properties of the new isolate, we conclude that strain OGL-20P(sup T) represents a new separate species within the genus Thermococcus, and propose the name Thermococcus thioreducens sp. nov. The type strain is OGL-20P(sup T) (= ATCC BAA-394(sup T) = JCM 12859(sup T) = DSM 14981(sup T)).