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At least 487 records · Page 27

Symposium on High Power, Ambient Temperature Lithium Batteries, 180th Meeting of the Electrochemical Society, Phoenix, AZ, Oct. 13-17, 1991, Proceedings

Papers presented in these proceedings are on the state of the art in high-power lithium batteries, a design analysis of high-power Li-TiS2 battery, the performance and safety features of spiral wound lithium/thionyl chloride cells, the feasibility of a superhigh energy density battery of the Li/BrF3 electrochemical system, and an enhanced redox process of disulfide compounds and their application in high energy storage. Attention is also given to the structure and charge-discharge characteristics of mesophase-pitch based carbons, a study of carbons and graphites as anodes for lithium rechargeable cells, Li metal-free rechargeable Li(1+x)Mn2O4/carbon cells, and rechargeable lithium batteries using V6O13/V5O5 as the positive electrode material. Other papers discuss the electrochemical stability of organic electrolytes in contact with solid inorganic cathode materials, the electrochemical behavior of methyl formate solutions, and the interface between a solid polymer electrolyte and lithium anode.

Clark, W. D. K.↗

Emissions of sulfur gases from marine and freshwater wetlands of the Florida Everglades - Rates and extrapolation using remote sensing

Rates of emissions of the biogenic sulfur (S) gases carbonyl sulfide (COS), methyl mercaptan (MSH), dimethyl sulfide (DMS), and carbon disulfide (CS2) were measured in a variety of marine and freshwater wetland habitats in the Florida Everglades during a short duration period in October using dynamic chambers, cryotrapping techniques, and gas chromatography. The most rapid emissions of over 500 nmol/sq m/h occurred in red mangrove-dominated sites that were adjacent to open seawater and contained numerous crab burrows. Poorly drained red mangrove sites exhibited lower fluxes of about 60 nmol/sq m/h, which were similar to fluxes from the black mangrove areas which dominated the marine-influenced wetland sites in the Everglades. DMS was the dominant organo-S gas emitted especially in the freshwater areas. Spectral data from a scene from the Landsat TM were used to map habitats in the Everglades. Six vegetation categories were delineated using geographical information system software and S gas emissions were extrapolated for the entire Everglades National Park. The black mangrove-dominated areas accounted for the largest portion of S gas emissions to the area. The large area extent of the saw grass communities accounted for about 24 percent of the total S emissions.

Hines, Mark E.↗

Component test results from the bearing life improvement program for the Space Shuttle Main Engine oxidizer turbopumps

Interim results from a component test program to improve ball bearing life in the Space Shuttle Main Engine oxygen turbopumps are presented. Two specific bearing applications, using liquid oxygen as the bearing coolant, are addressed. The first, the thrust bearing of the low pressure pump, operates at relatively slow speed with predominantly axial load and little temperature rise in the bulk coolant. Testing has demonstrated a very significant reduction in bearing wear by increasing the bearing internal clearance. Heat generation data was obtained that indicates heavy, intermittent cage-to-ball contact occurs, providing a possible explanation for the observed wear. The second application is the turbine end bearings of the high pressure pump. These bearings operate at high speed and load with the possibility of significant coolant vaporization. Tests on production bearings and bearings having modified internal clearance and curvature yielded scattered but generally poor lives. A dramatic improvement was achieved by coating the standard cage with a thin film of fluorinated ethylene propylene and 15 percent molybdenum disulfide. Very promising results have also been obtained by replacing the standard balls with ones made of silicon nitride, especially in combination with the coated cage.

Keba, John E.↗

Effect of Aging on Taut Rubber Diaphragms

As part of an investigation of special compositions of rubber suitable for use as diaphragms for aircraft instruments, six samples were used as taut diaphragms in instruments and allowed to age for five years. Two of the instruments were in operating condition after this period of time and one had remarkably little change in performance. In making the rubber tetraethyl thorium disulfide was employed as a vulcanizing agent.

Henrickson, H B↗

A preliminary study of the variability and magnitude of the flux of biogenic sulfur gases from a New Hampshire salt marsh

Salt marshes have highly variable spatial and temporal fluxes of hydrogen sulfide, carbonyl sulfide, methane thiol, dimethyl sulfide, and carbon disulfide (H2S, COS, MeSH, DMS, and CS2, respectively). This variability was tested at nine emission sites in a New Hampshire, USA salt marsh: three replicates in each of three vegetation zones, Spartina alterniflora, S. patens, and a transition zone. Three sites were sampled simultaneously, either within or across vegetation zones, using a dynamic flux chamber technique. Difficulties with calibration and field equipment resulted in fluxes with maximum absolute uncertainties of greater than plus or minus 200 percent. However, the relative uncertainty between subsequent samples was closer to plus or minus 20 percent. Chambers are expected to affect the natural flux of gases by altering the humidity, temperature, and composition of the gas inside the chamber. Summertime fluxes are highest for all gases except COS which demonstrated evidence of a springtime peak. A summertime background flux of 5 to 100 x 10(exp -9) g S/m(sup -2) min was observed for all gases, while S alternifora fluxes of MeSH and DMS were approximately 8 fold and approximately 100 fold higher than S. patens, respectively. DMS and MeSH fluxes were higher during the day than at night. Evidence of COS uptake by plants was observed. CS2 appeared to be the quantitatively least important sulfur gas emitted. Improved laboratory and sample collection techniques and further data collection in the field will yield information on the details of salt marsh variability, will improve estimates of the error associated with single flux measurements, and will allow a more accurate estimation of sulfur fluxes from salt marshes based on vegetation and area coverage data. Inability to control the temperature and humidity inside of the chamber remain significant problems with the chamber design.

Morrison, Michael Cope↗

Emissions of biogenic sulfur gases from Alaskan tundra

Fluxes of the biogenic sulfur gases carbonyl sulfide (COS), dimethyl sulfide (DMS), methyl mercaptan (MeSH), and carbon disulfide (CS2) were determined for several freshwater and coastal marine tundra habitats using a dynamic enclosure method and gas chromatography. In the freshwater tundra sites, highest emissions, with a mean of 6.0 nmol/m(sup -2)H(sup -1) (1.5-10) occurred in the water-saturated wet meadow areas inhabited by grasses, sedges, and Sphagnum mosses. In the drier upland tundra sites, highest fluxes occurred in areas inhabited by mixed vegetation and labrador tea at 3.0 nmol/m(sup -2)h(sup -1) (0-8.3) and lowest fluxes were from lichen-dominated areas at 0.9 nmol/m(sup -2)h(sup -1). Sulfur emissions from a lake surface were also low at 0.8 nmol/m(sup -2)h(sup -1). Of the compounds measured, DMS was the dominant gas emitted from all of these sites. Sulfure emissions from the marine sites were up to 20-fold greater than fluxes in the freshwater habitats and were also dominated by DMS. Emissions of DMS were highest from intertidal soils inhabited by Carex subspathacea (150-250 nmol/m(sup -2)h(sup -1)). This Carex sp. was grazed thoroughly by geese and DMS fluxes doubled when goose feces were left within the flux chamber. Emissions were much lower from other types of vegetation which were more spatially dominant. Sulfure emissions from tundra were among the lowest reported in the literature. When emission data were extrapolated to include all tundra globally, the global flux of biogenic sulfur from this biome is 2-3 x 10(exp 8) g/yr. This represents less than 0.001 percent of the estimated annual global flux (approximately 50 Tg) of biogenic sulfur and less than 0.01 percent of the estimated terrestrial flux. The low emissions are attributed to the low availability of sulfate, certain hydrological characteristics of tundra, and the tendency for tundra to accumulate organic matter.

Hines, Mark E.↗

Emissions of sulfur gases from marine and freshwater wetlands of the Florida Everglades: Rates and extrapolation using remote sensing

Rates of emissions of the biogenic sulfur (S) gases carbonyl sulfide (COS), methyl mercaptan (MSH), dimethyl sulfide (DMS), and carbon disulfide (CS2) were measured in a variety of marine and freshwater wetland habitats in the Florida Everglades during a short duration period in October using dynamic chambers, cryotrapping techniques, and gas chromatography. The most rapid emissions of greater than 500 nmol/m(sup -2)h(sup -1) occurred in red mangrove-dominated sites that were adjacent to open seawater and contained numerous crab burrows. Poorly drained red mangrove sites exhibited lower fluxes of approximately 60 nmol/m(sup -2)h(sup -1) which were similar to fluxes from the black mangrove areas which dominated the marine-influenced wetland sites in the Everglades. DMS was the dominant organo-S gas emitted especially in the freshwater areas. Spectral data from a scene from the Landsat thematic mapper were used to map habitats in the Everglades. Six vegetation categories were delineated using geographical information system software and S gas emission were extrapolated for the entire Everglades National Park. The black mangrove-dominated areas accounted for the largest portion of S gas emissions to the area. The large area extent of the saw grass communities (42 percent) accounted for approximately 24 percent of the total S emissions.

Hines, Mark E.↗

Status of the development of rechargeable lithium cells

The progress in the development of the ambient temperature lithium - titanium disulfide rechargeable cell under development at the Jet Propulsion Laboratory is described in this paper. Originally aimed at achieving a specific energy of 100 Wh/kg, 'AA' cells have demonstrated 125 Wh/kg at the C/3 discharge rate. The results of evaluating cell design parameters are discussed and cycling test data are also included in the paper. Safety tests results at various over-charge and over discharge conditions and rates proved to be uneventful. The test results of cell with built-in overcharge mechanism proved the concept was feasible. Replacing the lithium foil electrode with a Li(x)C resulted in a capacity at 1mA/cm(exp 2) of 200 mAh/gm and 235 mAh/gm at 0.167 mA.

Halpert, G.↗

Redetermination of piperidinium hydrogen sulfide structure

The presence of adventitious water in a reaction between dicyclopentamethylene thiuram-disulfide (C5H10NCS2)(sub 2) and a picoline solution of tricyclopentadienyl indium(III) (C5H5)(sub 3). It resulted in the formation of piperidinium hydrogen sulfide (C5H13NS). The piperidinium hydrogen sulfide produced in this way was unambiguously characterized by X-ray crystallography. The structure determination showed that the piperidinium hydrogen sulfide crystal (MW = 119.23 g/mol) has an orthorhombic (Pbcm) unit cell whose parameters are: a = 9.818(2), b = 7.3720(1), c = 9.754(1) A, V = 706.0(3) A(exp 3), Z=4. D(sub chi) = 1.122 g cm(exp -3), Mo K(alpha) (lamda = 0.71073), mu= 3.36 cm(exp -1), F(000) = 264.0, T =293 K, R = 0.036 for 343 reflections with F(sub O)(sup 2) greater than 3 sigma (F(sub O)(sup 2)) and 65 variables. The compound consists of (C5H10NH2)(+) cations and (SH)(-) anions with both species residing on crystallographic mirror planes. N-H -- S hydrogen bonding contributes to the interconnection of neighboring piperidinium components of the compound.

Andras, Maria T.↗

One-step synthesis of dithiocarbamates from metal powders

Neutral metal dithiocarbamate complexes (M(NR2CS2)X) are well-known precursors to metal sulfides, a class of materials with numerous technological applications. We are involved in a research effort to prepare new precursors to metal sulfides using simple, reproducible synthetic procedures. We describe the results of our synthetic and characterization studies for M = Fe, Co, Ni, Cu. and In. For example, treatment of metallic indium with tetramethylthiuram disulfide (tmtd) in 4-methylpyridine (4-Mepy) at 25 deg C produces a new homoleptic indium (III) dithiocarbamate, In(N(CH3)2CS2)3(I), in yields of over 60 percent. The indium (III) dithiocarbamate was characterized by X-ray crystallography; (I) exists in the solid state as discrete distorted-octahedral molecules. Compound (I) crystallizes in the P1bar (No. 2) space group with lattice parameters: a = 9.282(1) A, b = 10.081(1) A, c = 12.502 A, alpha = 73.91(1) deg, beta = 70.21(1) deg, gamma = 85.8(1)deg, and Z = 2. X-ray diffraction and mass spectral data were used to characterize the products of the analogous reactions with Fe, Co, Ni, and Cu. We discuss both use of dithiocarbamates as precursors and our approach to their preparation.

Hepp, Aloysius F.↗

An intercomparison of aircraft instrumentation for tropospheric measurements of sulfur dioxide

As part of the NASA Tropospheric Chemistry Program, a series of field intercomparisons have been conducted to evaluate the state-of-the art for measuring key tropospheric species. One of the objectives of the third intercomparison campaign in this series, Chemical Instrumentation Test and Evaluation 3 (CITE 3), was to evaluate instrumentation for making reliable tropospheric aircraft measurements of sulfur dioxide, dimethyl sulfide, hydrogen sulfide, carbon disulfide, and carbonyl sulfide. This paper reports the results of the intercomparisons of five sulfur dioxide measurement methods ranging from filter techniques, in which samples collected in flight are returned to the laboratory for analyses (chemiluminescent or ion chromatographic), to near real-time, in-flight measurements via gas chromatographic, mass spectrometric, and chemiluminescent techniques. All techniques showed some tendency to track sizeable changes in ambient SO2 such as those associated with altitude changes. For SO2 mixing ratios in the range of 200 pptv to a few ppbv, agreement among the techniques varies from about 30% to several orders of magnitude, depending upon the pair of measurements intercompared. For SO2 mixing ratios less than 200 pptv, measurements from the techniques are uncorrelated. In general, observed differences in the measurement of standards do not account for the flight results. The CITE 3 results do not unambiguously identify one or more of the measurement techniques as providing valid or invalid SO2 measurements, but identify the range of 'potential' uncertainty in SO2 measurements reported by currently available instrumentation and as measured under realistic aircraft environments.

Gregory, Gerald L.↗

Surface Chemistry, Friction, and Wear Properties of Untreated and Laser-Annealed Surfaces of Pulsed-Laser-Deposited WS(sub 2) Coatings

An investigation was conducted to examine the surface chemistry, friction, and wear behavior of untreated and annealed tungsten disulfide (WS2) coatings in sliding contact with a 6-mm-diameter 440C stainless-steel ball. The WS2 coatings and annealing were performed using the pulsed-laser-deposition technique. All sliding friction experiments were conducted with a load of 0.98 N (100 g), an average Hertzian contact pressure of 0.44 GPa, and a constant rotating speed of 120 rpm. The sliding velocity ranged from 31 to 107 mm/s because of the range of wear track radii involved in the experiments. The experiment was performed at room temperature in three environments: ultrahigh vacuum (vacuum pressure, 7X(exp -10) Pa), dry nitrogen (relative humidity, less than 1 percent), and humid air (relative humidity, 15 to 40 percent). Analytical techniques, including scanning electron microscopy (SEM), energy-dispersive x-ray spectroscopy (EDX), x-ray photo electron spectroscopy (XPS), surface profilometry, and Vickers hardness testing, were used to characterize the tribological surfaces of WS2 coatings. The results of the investigation indicate that the laser annealing decreased the wear of a WS2 coating in an ultrahigh vacuum. The wear rate was reduced by a factor of 30. Thus, the laser annealing increased the wear life and resistance of the WS2 coating. The annealed WS 2 coating had a low coefficient of friction (less than O.1) and a low wear rate ((10(exp -7) mm(exp 3)/N-m)) both of which are favorable in an ultrahigh vacuum.

Miyoshi, Kazuhisa↗

A Competitive Kinetics Study of the Reaction of Cl with CS2 in Air at 298 K

The relative rate technique has been used to investigate the kinetics of the reaction of Cl atoms with carbon disulfide, CS2, at 700 Torr total pressure of air at 298 K. The decay rate of CS2 was measured relative to CH4, CH3Cl and CHF2CL. For experiments using CH4 and CH3Cl references, the decay rate of CS2 was dependent on the ratio of the concentration of the reference to that of CS2. We ascribe this behavior to the generation of OH radicals in the system leading to complicated secondary chemistry. From experiments using CHF2Cl we are able to assign an upper limit of 4 x 10(exp -15) cu cm/(molecule s) for the overall reaction, Cl + CS2 yields products.

Wallington, Timothy J.↗

Sulfur and Hydrogen Isotope Anomalies in Meteorite Sulfonic Acids

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.

Cooper, George W.↗

Motor Brush Testing for Mars and Vacuum

Brush motors have been qualified and flown successfully on Mars missions, but upcoming missions require longer life and higher power. A test program was therefore undertaken to identify the best brush material for operation in the Mars atmosphere. Six different brush materials were used in 18 identical motors and operated under various load conditions for a period of four weeks in low-pressure CO2. All motors performed acceptably, with accumulated motor revolutions between 98 and 144 million revolutions, depending on load. A proprietary silver-graphite material from Superior Carbon (SG54-27) appears to be the best choice for long life, but even the stock copper-graphite brushes performed reliably with acceptable wear. The motors from the CO2 test were then cleaned and run in vacuum for 2 weeks. The difference in results was dramatic, with 5 motors failing catastrophically and wear rates increasing by orders of magnitude for the SG54-27 material. Three brush materials survived the test with no failures: SG54-27 with a proprietary Ball Aerospace impregnation, a silver-graphite-molybdenum disulfide material from Superior Carbon (SG59), and a copper sulfide-graphite material also from Superior Carbon (BG91).

Noon, Don E.↗

Friction and Wear Properties of Selected Solid Lubricating Films

To evaluate commercially developed solid film lubricants for aerospace bearing applications, we investigated the friction and wear behavior of bonded molybdenum disulfide (MoS2), magnetron-sputtered MoS2 and ion-plated silver films in sliding contact with 6-mm-diameter American Iron and Steel Institute (AISI) 440 C stainless steel balls. Unidirectional sliding friction experiments were conducted with a load of 5.9 N (600 g), a mean Herizian contact pressure of 0.79 GPa maximum 1.19 GPa), and a sliding velocity of 0.2 m/s at room temperature in three environments: ultrahigh vacuum (7x10 (exp -7Pa)), humid air (approx. 20 percent humidity), and dry nitrogen (less than 1 percent humidity). The resultant films were characterized by scanning electron microscopy, energy-dispersive x-ray spectroscopy, and surface profilometry. Marked differences in friction and wear resulted front the environmental conditions and the film materials. The main criteria for judging the performance were coefficient of friction and wear rate, which had to be less than 0.3 and on the order of 10 (exp -6mm exp 3/Nm or less), respectively. The bonded MoS2 and magnetron-sputtered MoS2 films met the criteria in all three environments. Also, the wear rates of the counterpart AISI 440 C stainless steel balls met that criterion in all three environments. The ion-plated silver films met the criteria only in ultrahigh vacuum. In ultrahigh vacuum the bonded MoS2 films were superior. In humid air the bonded MoS2 films had higher coefficient of friction and shorter wear life than did the magnetron-sputtered MoS2 films. The ion-plated silver films had a high coefficient of friction in humid air but relatively low coefficients of friction in the nonoxidative environments. Adhesion and plastic deformation played important roles in all three environments. All sliding involved adhesive transfer of materials.

Miyoshi, Kazuhisa↗

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↗

Evaluation of Selected Solid Lubricating Films

An investigation was conducted to examine the friction and wear properties of bonded molybdenum disulfide (MoS2), magnetron-sputtered MoS2, ion-plated silver, ion-plated lead, magnetron-sputtered diamondlike carbon (MS DLC), and plasma-assisted, chemical-vapor-deposited DLC (PACVD DLC) films in sliding contact with 6-mm-diameter AISI 440C stainless steel balls. Unidirectional ball-on-disk sliding friction experiments were conducted with a load of 5.9 N and a sliding velocity of 0.2 m/s at room temperature in three environments: ultrahigh vacuum (vacuum pressure, 7 x 10(exp -7) Pa), humid air (relative humidity, approx. 20 percent), and dry nitrogen (relative humidity, less than 1 percent). The main criteria for judging the performance of the solid lubricating films were coefficient of friction and wear rate, which had to be less than 0.3 and on the order of 10(exp -6) cubic mm/N(dot)m or less, respectively. The bonded MoS2 and magnetron-sputtered MoS2 films met the criteria in all three environments. The ion-plated lead and silver films met the criteria only in ultrahigh vacuum but failed in humid air and in dry nitrogen. The MS DLC and PACVD DLC films met the requirements in humid air and dry nitrogen but failed in ultrahigh vacuum.

Miyoshi, Kazuhisa↗