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At least 289 records · Page 16

Acidic attack of perfluorinated alkyl ether lubricant molecules by metal oxide surfaces

The reactions of linear perfluoropolyalkylether (PFAE) lubricants with alpha-Fe2O3 and Fe2O3-based solid superacids were studied. The reaction with alpha-Fe2O3 proceeds in two stages. The first stage is an initial slow catalytic decomposition of the fluid. This reaction releases reactive gaseous products which attach the metal oxide and convert it to FeF3. The second stage is a more rapid decomposition of the fluid, effected by the surface FeF3. A study of the inital breakdown step was performed using alpha-Fe2O3, alpha-Fe2O3 preconverted to FeF3, and sulfate-promoted alpha-Fe2O3 superacids. The results indicate that the breakdown reaction involves acidic attack at fluorine atoms on acetal carbons in the linear PFAE. Possible approaches to combat the problem are outlined.

Zehe, Michael J.↗

Degradation and crosslinking of perfluoroalkyl polyethers under X-ray irradiation in ultrahigh vacuum

Degradation of three types of commercially available perfluoroalkyl polyethers (PFPE)-Demnum S200, Fomblin Z25, and Krytox 16256-by X-ray irradiation was studied by using X-ray photoemission spectroscopy (XPS) and a mass spectrometer under ultra-high-vacuum conditions. The carbons in the polymers were characterized by chemical shifts of Cls binding energies. Gaseous products containing COF2 and low-molecular-weight fluorocarbons were formed. From Fomblin Z25, which has acetal linkages (-OCF2O-), a large quantity of COF2 gas was evolved. Liquid products became tacky after a long irradiation time, and some did not dissolve in Freon. High-pressure liquid chromatography (HPLC) showed that molecular weight distribution became broader and that higher molecular weight polymers were formed from Demnum and Krytox. We concluded from these results that degradation and cross-linking took place simultaneously. Demnum crosslinked more easily than the other fluids. The time dependence of both XPS spectra of Cls and mass spectra showed that C-O-bonded carbons in PFPE'S were removed faster than other carbons. There was no substrate effect on the degradation reaction because the first-order rate constants calculated from the change of gaseous products were similar when stainless steel (440C) and gold-coated surfaces were used. Metal fluorides were formed on stainless steel during the reaction. A mechanism for the degradation of PFPE'S is discussed on the basis of their molecular structures.

Mori, Shigeyuki↗

Reaction of perfluoroalkylpolyethers (PFPE) with 440C steel in vacuum under sliding conditions at room temperature

Reactions of perfluoroalkylpolyethers (PFPE: Fomblin, Demnum and Krytox) were studied during the sliding contact of stainless steel specimens under ultrahigh vacuum conditions. All three fluids reacted with the steel specimens during sliding. Fomblin, which has acetal linkages, decomposed under the sliding conditions generating gaseous products, (COF2 and fluorinated carbons) which were detected by a quadrupole mass spectrometer. Gaseous products were not detected for the Demnum and Krytox fluids. The amount of gaseous products from Fomblin increased with increasing sliding speed. At the end of the sliding experiments, the wear scar and deposits on the specimens were examined by small spot size XPS. The oxide layer on the specimen surface was removed during sliding, and metal fluorides were formed on the worn surface. The surface of the wear scar and deposits were covered with adsorbed PFPE. Based on these results, it was concluded that the decomposition reaction on Fomblin was initiated by contacting the fluid with a fresh metal surface which was formed during sliding.

Mori, Shigeyuki↗

Closure measurements on short fatigue cracks

Single-edged notched specimens, 2.3 mm thick, of 2024-T3 aluminum were cyclically loaded at R-ratios of 0.5, 0.0, -1.0, and -2.0. The notch roots were periodically inspected with an optical microscope to locate the initiation of very short cracks. Acetate replicas were also taken. The loads were selected to produce fatigue lives of 500,000 cycles or less. Crack opening displacements were measured at single positions across cracks as short as 0.035 mm and as long as the full thickness of the specimen. The opening load ratios for the short cracks are somewhat smaller than for long cracks at positive R-ratios, but are considerably smaller for negative R-ratios.

Lee, Joo-Jin↗

Chemokinetic motility responses of the cyanobacterium oscillatoria terebriformis

Oscillatoria terebriformis, a gliding, filamentous, thermophilic cyanobacterium, exhibited an inhibition of gliding motility upon exposure to fructose. The observed response was transient, and the duration of nonmotility was directly proportional to the concentration of fructose. Upon resumption of motility, the rate of motility was also inversely proportional to the concentration of fructose. Sulfide caused a similar response. The effect of sulfide was specific and not due to either anoxia or negative redox potential. Exposure to glucose, acetate, lactate, or mat interstitial water did not elicit any motility response.

Richardson, Laurie L.↗

Effects of microgravity on growth hormone concentration and distribution in plants

On earth, gravity affects the distribution of the plant growth hormone, indole-3-acetic acid (IAA), in a manner such that the plant grows into a normal vertical orientation (shoots up, roots down). How the plant controls the amount and distribution of IAA is only partially understood and is currently under investigation in this laboratory. The question to be answered in the flight experiment concerns the effect of gravity on the concentration, turn over, and distribution of the growth hormone. The answer to this question will aid in understanding the mechanism by which plants control the amount and distribution of growth hormone. Such knowledge of a plant's hormonal metabolism may aid in the growth of plants in space and will lead to agronomic advances.

Schulze, Aga↗

Fatigue crack initiation and small crack growth in several airframe alloys

The growth of naturally-initiated small cracks under a variety of constant amplitude and variable amplitude load sequences is examined for several airframe materials: the conventional aluminum alloys, 2024-T3 and 7075-T6, the aluminum-lithium alloy, 2090-T8E41, and 4340 steel. Loading conditions investigated include constant amplitude loading at R = 0.5, 0, -1 and -2 and the variable amplitude sequences FALSTAFF, Mini-TWIST and FELIX/28. Crack growth was measured at the root of semicircular edge notches using acetate replicas. Crack growth rates are compared on a stress intensity factor basis, to those for large cracks to evaluate the extent of the small crack effect in each alloy. In addition, the various alloys are compared on a crack initiation and crack growth morphology basis.

Swain, M. H.↗

Synthesis of Y1Ba2Cu3O(sub x) superconducting powders by intermediate phase reaction

One of the more striking problems for the synthesis of the Y1Ba2Cu3Ox compound is the high-temperature decomposition of the BaCO3. This compound is present as raw material or as an intermediate compound in chemical processes such as amorphous citrate, coprecipitation oxalate, sol-gel process, acetate pyrolisis, etc. This fact makes difficult the total formation reaction of the Y1Ba2Cu3Ox phase and leads to the presence of undesirable phases such as the BaCuO2 phase, the 'green phase', Y2BaCuO5 and others. Here, a new procedure to overcome this difficulty is studied. The barium cation is previously combined with yttrium and/or copper to form intermediate compounds which can react between them to give Y1Ba2Cu3Ox. BaY2O4 and BaCu2O3 react according to the equation BaY2O4+3BaCu2O3 yields 2Y1Ba2Cu3Ox. BaY2O4 is a stable compound of the Y2O3-BaO system; BaCu2O3 is an intimate mixture of BaCuO2 and uncombined CuO. The reaction kinetics of these phases have been established between 860 and 920 C. The phase evolution has been determined. The crystal structure of the Y1Ba2Cu3Ox obtained powder was studied. According to the results obtained from the kinetics study the Y1Ba2Cu3Ox the synthesis was performed at temperatures of 910 to 920 C for short treatment times (1 to 2 hours). Pure Y1Ba2Cu3Ox was prepared, which develops orthorombic type I structure despite of the cooling cycle. Superconducting transition took place at 91 K. The sintering behavior and the superconducting properties of sintered samples were studied. Density, microstructure and electrical conductivity were measured. Sintering densities higher than 95 percent D(sub th) were attained at temperatures below 940 C. Relatively fine grained microstructure was observed, and little or no-liquid phase was detected.

Moore, C.↗

Subcritical and supercritical water oxidation of CELSS model wastes

A mixture of ammonium hydroxide with acetic acid and a slurry of human feces, urine, and wipes were used as CELSS model wastes to be wet-oxidized at temperatures from 250 to 500 C, i.e. below and above the critical point of water (374 C and 218 kg/sq cm or 21.4 MPa). The effects of oxidation temperature ( 250-500 C) and residence time (0-120 mn) on carbon and nitrogen and on metal corrosion from the reactor material were studied. Almost all of the organic matter in the model wastes was oxidized in the temperature range from 400 to 500 C, above the critical conditions for water. In contrast, only a small portion of the organic matter was oxidized at subcritical conditions. A substantial amount of nitrogen remained in solution in the form of ammonia at temperatures ranging from 350 to 450 C suggesting that, around 400 C, organic carbon is completely oxidized and most of the nitrogen is retained in solution. The Hastelloy C-276 alloy reactor corroded during subcritical and supercritical water oxidation.

Takahashi, Y.↗

The effects of fire on biogenic emissions of methane and nitric oxide from wetlands

Enhanced emissions of methane (CH4) and nitric oxide (NO) were measured following three controlled burns in a Florida wetlands in 1987 and 1988. Wetlands are the major global source of methane resulting from metabolic activity of methanogenic bacteria. Methanogens require carbon dioxide, acetate, or formate for their growth and the metabolic production of methane. All three water-soluble compounds are produced in large concentrations during biomass burning. Postfire methane emissions exceeded 0.15 g CH 4/sq m per day. Preburn and postburn measurements of soil nutrients indicate significant postburn increases in soil ammonium, from 8.35 to 13.49 parts per million (ppm) in the upper 5 cm of the Juncus marsh and from 8.83 to 23.75 ppm in the upper 5 cm of the Spartina marsh. Soil nitrate concentrations were found to decrease in both marshes after the fire. These measurements indicate that the combustion products of biomass burning exert an important 'fertilizing' effect on the biosphere and on the biogenic production of environmentally significant atmospheric gases.

Levine, Joel S.↗

Decomposition of perfluoroalkylpolyethers (PFPE) in ultra-high vacuum under sliding conditions

Reactions of perfluoroalkylpolyethers (PFPE: Fomblin, Demnum and Krytox) were studied during the sliding contact of stainless steel specimens under ultrahigh vacuum conditions. All three fluids reacted with the steel specimens during sliding. Fomblin, which has acetal linkages, decomposed under the sliding conditions generating gaseous products, (COF2 and fluorinated carbons) which were detected by a quadrupole mass spectrometer. Gaseous products were not detected for the Demnum and Krytox fluids. The amount of gaseous products from Fomblin increased with increasing sliding speed. At the end of the sliding experiments, the wear scar and deposits on the specimens were examined by small spot size XPS. The oxide layer on the specimen surface was removed during sliding, and metal fluorides were formed on the worn surface. The surface of the wear scar and deposits were covered with adsorbed PFPE. Based on these results, it was concluded that the decomposition reaction on Fomblin was initiated by contacting the fluid with a fresh metal surface which was formed during sliding.

Mori, Shigeyuki↗

Rainfall and surface kinematic conditions over central amazonia during ABLE 2B

Rainfall, rainfall systems, and surface kinematics of the central Amazon basin wet season are investigated using meteorological and chemical data collected during the wet season Amazon Boundary Layer Experiment (ABLE) near Manaus, Brazil. Through analysis of (GOES-West) imagery, it is determined that, based on location of the initial development, there are three main types of convective systems which influence a mesoscale network near Manaus, namely the Coastal Occurring Systems (COS), the Basin Occurring Systems (BOS), and the Locally Occurring Systems (LOS). Chemical analysis of rainwater delivered by these systems shows significant differences in concentrations of formate, acetate, pyruvate, sulfate, and hydrogen ion, and measurements of aerosol concentrations near Manaus show large influxes of aerosols into central Amazonia after passage of BOS and COS. Results of satellite based classification of the rain-producing systems are discussed.

Greco, Steven↗

Impregnating Coal With Calcium Carbonate

Relatively inexpensive process proposed for impregnating coal with calcium carbonate to increase rates of gasification and combustion of coal and to reduce emission of sulfur by trapping sulfur in calcium sulfide. Process involves aqueous-phase reactions between carbon dioxide (contained within pore network of coal) and calcium acetate. Coal impregnated with CO2 by exposing it to CO2 at high pressure.

Sharma, Pramod K.↗

The growth of short cracks in 4340 steel and aluminum-lithium 2090

The objectives were to investigate crack initiation characteristics and short crack growth behavior for Al-Li 2090 and for 4340 steel and to evaluate the ability of a closure-based crack-growth model to predict fatigue crack growth rates and total fatigue lives for the steel. Single-edge-notched tension specimens of each alloy were used to obtain the short crack growth rate information via an acetate replica technique. In addition to constant amplitude loading, tests on the steel were conducted using the Felix/28 variable amplitude spectrum (a shortened form of a standard loading sequence for fixed or semi-rigid helicopter rotors). The short crack growth rates were compared to those for long cracks grown under similar loading conditions. Metallurgical features associated with crack initiation are discussed. For Al-Li 2090 under R = -1 loading, the short cracks grew well below the long crack threshold and grew at acute angles to the loading axis. For 4340 steel under constant amplitude loading at R = 0.5 and 0 and for the Felix/28 spectrum loading, short-crack growth rates agreed well with long-crack growth rates, even near the long-crack threshold. A slight short-crack effect, growth below the long-crack threshold, was observed at R = -1. Fatigue lives were found to depend on the size and type of initiation site, especially for the Felix/28 loading sequence. A semi-empirical crack-growth model incorporating crack-closure effects was used to predict crack growth rates and total fatigue lives of notched 4340 steel specimens. An initial defect size and shape typical of those identified in this steel was assumed for the life predictions. For all loading conditions, reasonable agreement was found between measured and predicted values for both crack growth rates and fatigue lives.

Swain, M. H.↗

High Tc superconducting materials and devices

The high Tc Y1Ba2Cu3O(7-x) ceramic materials, initially developed in 1987, are now being extensively investigated for a variety of engineering applications. The superconductor applications which are presently identified as of most interest to NASA-LaRC are low-noise, low thermal conductivity grounding links; large-area linear Meissner-effect bearings; and sensitive, low-noise sensors and leads. Devices designed for these applications require the development of a number of processing and fabrication technologies. Included among the technologies most specific to the present needs are tapecasting, melt texturing, magnetic field grain alignment, superconductor/polymer composite fabrication, thin film MOD (metal-organic decomposition) processing, screen printing of thick films, and photolithography of thin films. The overall objective of the program was to establish a high Tc superconductivity laboratory capability at NASA-LaRC and demonstrate this capability by fabricating superconducting 123 material via bulk and thin film processes. Specific objectives include: order equipment and set up laboratory; prepare 1 kg batches of 123 material via oxide raw material; construct tapecaster and tapecaster 123 material; fabricate 123 grounding link; fabricate 123 composite for Meissner linear bearing; develop 123 thin film processes (nitrates, acetates); establish Tc and Jc measurement capability; and set up a commercial use of space program in superconductivity at LaRC. In general, most of the objectives of the program were met. Finally, efforts to implement a commercial use of space program in superconductivity at LaRC were completed and at least two industrial companies have indicated their interest in participating.

Haertling, Gene H.↗

Localize and identify the gravity sensing mechanism of plants

The machinery by which a plant transduces the gravity stimulus into a growth response is localized and identified at the cellular level. The fact that a plant grows unequally on the lower side of a horizontally placed stem implies that there must be an asymmetric distribution of some of the chemical substances involved in the growth response. The three most likely chemicals to cause this growth were determined to be potassium, calcium, or the growth hormone, indole-3-acetic acid (IAA). IAA was chosen for this study and the results present a fairly complete understanding of the transduction of the gravity stimulus.

Bandurski, Robert S.↗

Acidic attack of perfluorinated alkyl ether lubricant molecules by metal oxide surfaces

The reactions of linear perfluoropolyalkylether (PFAE) lubricants with alpha-Fe203 and Fe203-based solid superacids were studied. The reaction with alpha-Fe203 proceeds in two stages. The first stage is an initial slow catalytic decomposition of the fluid. This reaction releases reactive gaseous products which attach the metal oxide and convert it to FeF3. The second stage is a more rapid decomposition of the fluid, effected by the surface FeF3. A study of the initial breakdown step was performed using alpha-Fe203, alpha-Fe203 preconverted to FeF3, and sulfate-promoted alpha-Fe203 superacids. The results indicate that the breakdown reaction involves acidic attack at fluorine atoms on acetal carbons in the linear PFAE. Possible approaches to combat the problem are outlined.

Zehe, Michael J.↗

Protein solubilities determined by a rapid technique and modification of that technique to a micro-method

A simple, rapid method for determination of protein solubilities has been developed which is based upon maximization of the free solution volume to be brought into equilibrium. The tetragonal lysozome solubility diagram has been determined from pH 4.0 to 5.2 (0.1 M sodium acetate), 2-7 percent NaCl, 3-25 C, and portions of the orthorhombic solubility diagram using this technique. Both tetragonal and orthorhombic solubilities were found to increase smoothly with decreasing salt concentration and increasing temperature; no retrograde solubilities were observed. Using column volumes of 75, 300, and 900 microliters, identical tetragonal lysozyme solubility diagrams were obtained. Chymotrypsinogen solubilities have also been determined using this apparatus, being retrograde over the temperature range tested. It is noted that the primary limiting factor in reducing the crystalline volume is the minimum solution sample size needed to accurately quantitate the protein.

Cacioppo, Elizabeth↗