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At least 289 records · Page 16

Surfactant/Supercritical Fluid Cleaning of Contaminated Substrates

CFC's and halogenated hydrocarbon solvents have been the solvents of choice to degrease and otherwise clean precision metal parts to allow proper function. Recent regulations have, however, rendered most of these solvents unacceptable for these purposes. New processes which are being used or which have been proposed to replace these solvents usually either fail to remove water soluble contaminants or produce significant aqueous wastes which must then be disposed of. In this work, a new method for cleaning surfaces will be investigated. Solubility of typical contaminants such as lubricating greases and phosphatizing bath residues will be studied in several surfactant/supercritical fluid solutions. The effect of temperature, pressure, and the composition of the cleaning mixture on the solubility of oily, polar, and ionic contaminants will be investigated. A reverse micellar solution in a supercritical light hydrocarbon solvent will be used to clean samples of industrial wastes. A reverse micellar solution is one where water is dissolved into a non-polar solvent with the aid of a surfactant. The solution will be capable of dissolving both water-soluble contaminants and oil soluble contaminants. Once the contaminants have been dissolved into the solution they will be separated from the light hydrocarbon and precipitated by a relatively small pressure drop and the supercritical solvent will be available for recycle for reuse. The process will be compared to the efficacy of supercritical CO2 cleaning by attempting to clean the same types of substrates and machining wastes with the same contaminants using supercritical CO2. It is anticipated that the supercritical CO2 process will not be capable of removing ionic residues.

White, Gary L.↗

Heterogeneous Uptake and Conversion of HOBr on H2SO4 at Upper Tropospheric and Stratospheric Temperatures (255 - 210 K)

Halogen species are known to catalytically destroy ozone in several different regions of the atmosphere. In addition to directly destroying ozone, bromine compounds can indirectly enhance ozone loss through coupling to other radical families. Hypobromous acid (HOBr), a key species in the linkage of BrOx to ClOx and HOx, is produced by the hydrolysis of BrONO2 on sulfate aerosols, and thus the heterogeneous behavior of HOBr must be understood. We have measured the solubility of HOBr in 45 to 70 percent by weight sulfuric acid solutions. Over the temperature range 208 to 255 K, HOBr is very soluble in sulfuric acid, H(*) = 10(exp 4) to 10(exp 8) M/atm. The solubility is temperature dependent, and our results agree well with those of Waschewsky and Abbott for 60 percent by weight H2SO4. HOBr is nearly as soluble as HBr, indicating that equilibrium concentrations of HOBr could approach those of HBr in sulfuric acid aerosols. Despite the high solubility of HOBr, stratospheric aerosol volumes are not large enough to sequester a significant fraction of inorganic bromine from the gas phase. Uptake of HOBr was nearly always accompanied by reaction, producing Br2O and possibly Br2. The effect of this bromine conversion pathway on the HOx and ClOx families, particularly at temperatures as warm as 255 K, will be considered.

Iraci, Laura T.↗

Characterization of the association of nitrate reductase with barley (Hordeum vulgare L.) root membranes

The nature of the association between nitrate reductase (NR) and membranes was examined. Nitrate reductase activity (NRA) associated with the microsomal fraction of barley (Hordeum vulgare L.) roots amounted to 0.6 to 0.8% of soluble NRA following sonication in the presence of 250 mM KI and repeated osmotic shock. This treatment removed all contaminating soluble NRA from microsomes of uninduced barley roots that had been homogenized in a soluble extract from roots of NO3(-)-induced plants. On continuous sucrose gradients, NRA co-migrated specifically with VO4(-)-sensitive ATPase activity, a plasma membrane (PM) marker; activity of glucose-6-phosphate dehydrogenase, assayed as cytosolic marker, co-migrated with NRA. Microsomal NRA was absent in barley deficient in soluble NR. Perturbation and trypsinolysis experiments with PM vesicles isolated by aqueous two-phase partitioning indicated that NR is associated with the periphery of the cytoplasmic face of the bilayer. These results demonstrate that PM and soluble NRs are essentially the same protein but that the membrane-associated form is tightly bound. Although it is possible that PM-associated NR exists in vivo, unequivocal evidence for this has yet to be shown. However, PM NR is definitely present in vitro.

Non-NASA Center↗

Uptake and Dissolution of Gaseous Ethanol in Sulfuric Acid

The solubility of gas-phase ethanol (ethyl alcohol, CH3CH2OH, EtOH) in aqueous sulfuric acid solutions was measured in a Knudsen cell reactor over ranges of temperature (209-237 K) and acid composition (39-76 wt % H2SO4). Ethanol is very soluble under these conditions: effective Henry's law coefficients, H*, range from 4 x 10(exp 4) M/atm in the 227 K, 39 wt % acid to greater than 10(exp 7) M/atm in the 76 wt % acid. In 76 wt % sulfuric acid, ethanol solubility exceeds that which can be precisely determined using the Knudsen cell technique but falls in the range of 10(exp 7)-10(exp 10) M/atm. The equilibrium concentration of ethanol in upper tropospheric/lower stratospheric (UT/LS) sulfate particles is calculated from these measurements and compared to other small oxygenated organic compounds. Even if ethanol is a minor component in the gas phase, it may be a major constituent of the organic fraction in the particle phase. No evidence for the formation of ethyl hydrogen sulfate was found under our experimental conditions. While the protonation of ethanol does augment solubility at higher acidity, the primary reason H* increases with acidity is an increase in the solubility of molecular (i.e., neutral) ethanol.

Michelsen, Rebecca R.↗

Organic Analysis in the Miller Range 090657 CR2 Chondrite: Part 3 C and N Isotopic Imaging

Primitive carbonaceous chondrites contain a wide variety of organic material, ranging from soluble discrete molecules to insoluble nanoglobules of macro-molecular carbon. The relationship between the soluble organic molecules, macromolecular organic material, and host minerals are poorly understood. Large H, C and N isotopic anomalies suggest some organic components formed in low-T interstellar or outer Solar System environments. The highest isotope anomalies occur in m-scale inclusions in the most primitive materials, such as cometary dust and the least altered carbonaceous chondrites. Often, the hosts of these isotopically anomalous 'hotspots' are discrete organic nanoglobules that probably formed in the outermost reaches of the protosolar disk or cold molecular cloud. Molecular and isotopic studies of meteoritic organic matter are aimed at identifying the chemical properties and formation processes of interstellar organic materials and the subsequent chemical evolutionary pathways in various Solar System environments. The combination of soluble and insoluble analyses with in situ and bulk studies provides powerful constraints on the origin and evolution of organic matter in the Solar System. Using macroscale extraction and analysis techniques as well as microscale in situ observations we have been studying both insoluble and soluble organic material in primitive astromaterial samples. Here, we present results of bulk C and N isotopic measurements and coordinated in situ C and N isotopic imaging and mineralogical and textural studies of carbonaceous materials in a Cr2 carbonaceous chondrite. In accompanying abstracts we discuss the morphology and distribution of carbonaceous components and soluble organic species of this meteorite.

Messenger, S.↗

Quantitation of buried contamination by use of solvents. Part 1: Solvent degradation of amine cured epoxy resins

The solubility and/or swelling of cured epoxy resins was studied using the solubility parameter method. Determination of solubility parameters were found in order to select solvents for solvent-assisted degradation of cured epoxy polymers used in spacecraft. A method for improving recovery of seeded spores is suggested for assay of buried contaminants. Three commercial epoxy resins were cured using four different alkyl amines. For each resin-amine combination, three levels of amine were used, corresponding to 1/3, 2/3, and all of the amine required to react with the oxirane groups of the resin. The solubility parameters of the 36 resulting model compounds were determined in poorly and moderately hydrogen-bonded solvents. No strongly hydrogen-bonded solvents caused dissolution or swelling. The tolerance of cured resins is discussed in terms of polymer structure.

Rheineck, A. E.↗

Gas-rich minerals in the Allende meteorite - Attempted chemical characterization

A ten-step etching experiment with HNO3 was performed on a chromite-carbon residue from Allende, in order to characterize the HNO3-soluble minor phase 'Q' that contains most of the primordial Ar, Kr, and Xe. Each etch fraction was analyzed by neutron activation analysis for Cr, Fe, Co, Ir, and Au. The results suggest that Q consists of two minerals, each comprising about 5 per cent of the residue. Phase Q1, of Fe/Cr ratio greater than 20, is soluble in cold dilute HNO3 and seems to contain most of the heavy noble gases. It may be an HCl-insoluble sulfide of nominal composition (Fe84Ni12Cr4)Sx. Phase Q2, of Fe/Cr ratio about 0.5 and somewhat enriched in Co, is slowly soluble in hot concentrated HNO3 and seems to be at least an order of magnitude poorer in heavy noble gases than Q1. It may be daubre-elite or an acid-soluble variety of chromite.

Gros, J.↗

Synthesis of improved polyester resins

Eighteen aromatic unsaturated polyester prepolymers prepared by a modified interfacial condensation technique were investigated for their solubility in vinyl monomers and ability to provide high char yield forming unsaturated polyester resins. The best resin system contained a polyester prepolymer of phthalic, fumaric and diphenic acids reacted with 2,7-naphthalene diol and 9,9-bis(4-hydroxyphenyl)fluorene. This prepolymer is very soluble in styrene, divinyl benzene, triallyl cyanurate, diallyl isophthalate and methylvinylpyridine. It provided anaerobic char yields as high as 41 percent at 800 C. The combination of good solubility and char yield represents a significant improvement over state-of-the-art unsaturated polyester resins. The majority of the other prepolymers had only low or no solubility in vinyl monomers. Graphite composites from this prepolymer with styrene were investigated. The cause for the observed low shear strengths of the composites was not determined, however 12-week aging of the composites at 82 C showed that essentially no changes in the composites had occurred.

Mcleod, A. H.↗

Chemical weathering and diagenesis of a cold desert soil from Wright Valley, Antarctica - An analog of Martian weathering processes

Weathering, diagenesis, and chemical alteration of a soil profile from the Dry Valleys of Antarctica are investigated as an analog to soil development within the Martian regolith. Soil samples from a soil pit one meter deep on Prospect Mesa, Wright Valley, are examined for their major element concentrations, water-soluble cations and anions, carbon, sulfur, and water concentrations, and related petrographic characteristics of weathering in a cold, dry environment. A petrographic study of the samples suggests that most silicate mineral and lithic fragments exhibit some degree of alteration. Chemical alteration occurs both in samples above and within the permanently frozen zone. The concentrations of water-soluble cations, for example, Na(+), K(+), Ca(2+), and anions, Cl(-), SO4(2-), NO3(-), are found to decrease significantly from the surface to the permanently frozen zone, suggesting a major movement of water-soluble species. It is also found that enrichments in secondary mineral abundances correlate with the water soluble ion concentrations. The formation of zeolites is seen throughout the soil column; these, it is thought, may be reservoirs for volatile storage within the regolith.

Gibson, E. K.↗

Aluminum chloride formation on Space Shuttle aluminum oxide

Samples of particulates collected from the exhaust of Space Shuttle launches STS-1, -4, -5, -6, and -7 were analyzed. Scanning electron microscopy and X-ray diffractometry of these samples indicated that the particulates were spherical and predominantly composed of aluminum oxide. The water-soluble weight fraction, pH, acid-soluble weight fraction, and insoluble weight fraction were determined for each sample. Water-soluble weight fractions averaged about 7 percent of the total sample weight, were generally very acidic, and contained significantly elevated concentrations of chloride and aluminum (III) ion. The high concentrations of soluble aluminum (III) and chloride ions observed suggested that aluminum chlorides and/or oxychlorides had formed on the surface of the alumina particulates. More than 72 percent by weight of each sample was insoluble in either water or strong mineral acid, and was identified as alpha-Al2O3. The results from these analyses suggest that the surface of Space Shuttle exhaust alumina particulates will be highly acidic and heavily chlorided, and that a substantial amount of the surface chloride may be chemically associated with aluminum (III) ions rather than just physically adsorbed as HCl.

Cofer, W. R., III↗

The rainout parameterization in a photochemical model

Photochemical models of tropospheric trace species typically simulate the effects of wet removal of soluble species from the atmosphere through a first-order rainout parameterization, which is independent of the species solubility and constant in time. In this work a modified first-order rainout parameterization is proposed that is a function of the species' solubility and takes into account the intermittent nature of atmospheric wet removal. In the case of a highly soluble species, such as HNO3, the inclusion of the effects of intermittent rainout in the parameterization leads to averaged rainout lifetimes considerably higher than ones used in most photochemical models. For illustrative purposes this parameterization is applied to a one-dimensional steady state model with parameterized eddy diffusion, although in principle it can be used in more sophisticated multidimensional models. The model results are compared to analagous calculations obtained with a 3-D tracer transport model.

Giorgi, F.↗

Polyimides containing oxyethylene units. Part 4: Polymerization of dianhydrides containing ether linkages

The development of new composite resins for various aerospace applications is attempted. Although it is highly desirable that these polymers be soluble in order to facilitate processing, they must display considerable solvent-resistance in use. A recent approach has involved the synthesis of a new series of polyimides containing flexible linkages. The polymers were prepared by the polymerization of aromatic dianhydrides with diamines containing oxyethylene linkages. For example, the polymerization of 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) with 1,2-bis(4-aminophenoxy)ethane (1a) and bis2-(4-aminophenoxy)ethylether (lb), afforded highly crystalline polyimides that were completely insoluble. However, a polyimide that was amorphous and soluble was obtained from the polymerization of BTDA and an isomer of lb, i.e., bis2-(3-aminophenoxy)ethyl ether (4b). In an attempt to obtain a soluble, amorphous polyimide that could be annealed into a crysalline state, block copolymers of 1b and 4b and BTDA were prepared. Copolymers containing less than 20 weight % 1b were soluble in organic solvents. However, these polymers did not crystallize when heated above their Tg's. Copolymers containing higher levels of 1b were semicrystalline and insoluble. The polymerization of the diamines containing oxyethylene linkages with 4,4'-oxydiphthalic anhydride (ODPA) and a new dianhydride, i.e., 4,4'-oxyethyleneoxyethyleneoxydiphthalic anhydride (OEDA) was investigated. It was postulated that the use of these more flexible dianhydrides would result in more processable polyimides.

Harris, F. W.↗

Chemical investigation of Titan and Triton tholins

We report chromatographic and spectroscopic analyses of both Titan and Triton tholins, organic solids made from the plasma irradiation of 0.9:0.1 and 0.999:0.001 N2/CH4 gas mixtures, respectively. The lower CH4 mixing ratio leads to a nitrogen-richer tholin (N/C greater than 1), probably including nitrogen heterocyclic compounds. Unlike Titan tholin, bulk Triton tholin is poor in nitriles. From high-pressure liquid chromatography, ultraviolet and infrared spectroscopy, and molecular weight estimation by gel filtration chromatography, we conclude that (1) several H2O-soluble fractions, each with distinct UV and IR spectral signatures, are present, (2) these fractions are not identical in the two tholins, (3) the H2O-soluble fractions of Titan tholins do not contain significant amounts of nitriles, despite the major role of nitriles in bulk Titan tholin, and (4) the H2O-soluble fractions of both tholins are mainly molcules containing about 10 to 50 (C + N) atoms. We report yields of amino acids upon hydrolysis of Titan and Triton tholins. Titan tholin is largely insoluble in the putative hydrocarbon lakes or oceans on Titan, but can yield the H2O-soluble species investigated here upon contact with transient (e.g., impact-generated) liquid water.

Mcdonald, Gene D.↗

Incineration as a Method for Resource Recovery from Inedible Biomass in a Controlled Ecological Life Support System

Resource recovery from waste streams in a space habitat is essential to minimize the resupply burden and achieve self-sufficiency. In a Controlled Ecological Life Support System (CELSS) human wastes and inedible biomass will represent significant sources of secondary raw materials necessary for support of crop plant production (carbon, water, and inorganic plant nutrients). Incineration, pyrolysis, and water extraction have been investigated as candidate processes for recovery of these important resources from inedible biomass in a CELSS. During incineration CO2 is produced by oxidation of the organic components and this product can be directly utilized by plants. Water is concomitantly produced, requiring only a phase change for recovery. Recovery of inorganics is more difficult, requiring solubilization of the incinerator ash. The process of incineration followed by water solubilization of ash resulted in loss of 35% of the inorganics originally present in the biomass. Losses were attributed to volatilization (8%) and non-water-soluble ash (27%). All of the ash remaining following incineration could be solubilized with acid, with losses resulting from volatilization only. The recovery for individual elements varied. Elemental retention in the ash ranged from 100% of that present in the biomass for Ca, P, Mg, Na, and Si to 10% for Zn. The greatest water solubility was observed for potassium with recovery of approximately 77% of that present in the straw. Potassium represented 80% of the inorganic constituents in the wheat straw, and because of slightly greater solubility made up 86% of the water-soluble ash. Following incineration of inedible biomass from wheat, 65% of the inorganics originally present in the straw were recovered by water solubilization and 92% recovered by acid solubilization. Recovery of resources is more complex for pyrolysis and water extraction. Recovery of carbon, a resource of greater mass than the inorganic component of biomass, is more difficult following pyrolysis and water extraction of biomass. In both cases, additional processors would be required to provide products equivalent to those resulting from incineration alone. The carbon, water, and organic resources of inedible biomass are effectively separated and output in usable forms through incineration.

Bubenheim, David L.↗

An Extraordinary Accumulation of (-)-Pinoresinol in Cell-Free Extracts of Forsythia intermedia: Evidence for Enantiospecific Reduction of (+)-Pinoresinol

Stereoselective and enantiospecific transformation mechanisms in lignan biogenesis are only now yielding to scientific inquiry: it has been shown that soluble cell-free preparations from Forsythia intermedia catalysis the formation of the enantiomerically pure lignan, (-)-secoisolariciresinol, when incubated with coniferyl alcohol in the presence of NAD(P)H and H2O2. Surprisingly, (-)-pinoresinol also accumulates in this soluble cell-free assay mixture in greater than 96% enantiomeric excess, even though it is not the naturally occurring antipode present in Forsythia sp. But these soluble cell-free preparations do not engender stereoselective coupling; instead, racemic pinoresinols are first formed, catalysed by an H2O2-dependent peroxidase reaction. An enantiospecific NAD(P)H reductase then converts (+)- pinoresinol, and not the (-)-antipode, into (-)-secoisolariciresinol. Stereoselective syntheis of(+)-pinoresinol from E-coniferyl alcohol is, however, catalysed by an insoluble enzyme preparation in F. suspensa, obtained following removal of readily soluble and ionically bound enzymes; no exogenously supplied cofactors were required other than oxygen, although the reaction was stimulated by NAD-malate addition. Thus, the overall biochemical pathway to enantiomerically pure (-)-secoisolariciresinol has been delineated.

Katayama, Takeshi↗

Surfactant Facilitated Spreading of Aqueous Drops on Hydrophobic Surfaces

Microgravity technologies often require aqueous phases to spread over nonwetting hydrophobic solid/surfaces. At a hydrophobic surface, the air/hydrophobic solid tension is low, and the solid/aqueous tension is high. A large contact angle forms as the aqueous/air tension acts together with the solid/air tension to balance the large solid/aqueous tension. The aqueous phase, instead of spreading, is held in a meniscus by the large angle. Surfactants facilitate the wetting of water on hydrophobic surfaces by adsorbing on the water/air and hydrophobic solid/water interfaces and lowering the surface tensions of these interfaces. The tension reductions decrease the contact angle, which increases the equilibrium wetted area. Hydrocarbon surfactants (i.e. amphiphiles with a hydrophobic chain of methylene groups attached to a large polar group to give aqueous solubility) do not reduce significantly the contact angles of the very hydrophobic surfaces such as parafilm or polyethylene. Trisiloxane surfactants (amphiphiles with a hydrophobe consisting of methyl groups linked to a trisiloxane backbone in the form of a disk ((CH3)3-Si-O-Si-O-Si(CH3)3)) and an extended ethoxylate (-(OCH2CH2)n-) polar group in the form of a chain with seven or eight units) can significantly reduce the contact angle of water on a very hydrophobic surface and cause rapid and complete (or nearly complete) spreading (lermed superspreading). The overall goal of the research described in this proposal is to establish and verify a theory for how trisiloxanes cause superspreading, and then use this knowledge as a guide to developing more general hydrocarbon based surfactant systems which superspread and can be used in microgravity. We propose that the trisiloxane surfactants superspread when the siloxane adsorbs, the hydrophobic disk parts of the molecule adsorb onto the surface removing the surface water. Since the cross sectional area of the disk is larger than that of the extended ethoxylate chain, the disks can form a space filling mat on the surface which removes a significant amount of the surface water. The water adjacent to the hydrophobic solid surface is of high energy due to incomplete hydrogen bonding; its removal significantly lowers the tension and reduces the contact angle. Hydrocarbon surfactants cannot remove as much surface water because their large polar groups prevent the chains from cohering lengthwise. In our report last year we presented a poster describing the preparation of model very hydrophobic surfaces which are homogeneous and atomically smooth using self assembled monolayers of octadecyl trichlorosilane (OTS). In this poster we will use these surfaces as test substrates in developing hydrocarbon based surfactant systems which superspread. We studied a binary hydrocarbon surfactant systems consisting of a very soluble large polar group polyethylene oxide surfactant (C12E6 (CH3(CH2)11(OCH2CH2)6OH) and a long chain alcohol dodecanol. By mixing the alcohol with this soluble surfactant we have found that the contact angle of the mixed system on our test hydrophobic surfaces is very low. We hypothesize that the alcohol fills in the gaps between adjacent adsorbed chains of the large polar group surfactant. This filling in removes the surface water and effects the decrease in contact angle. We confirm this hypothesis by demonstrating that at the air/water interface the mixed layer forms condensed phases while the soluble large polar group surfactant by itself does not. We present drop impact experiments which demonstrate that the dodecanol/C12E6 mixture is effective in causing impacting drops to spread on the very hydrophobic model OTS surfaces.

Kumar, Nitin↗

Very, Very Fast Wetting

Just after formation, optical fibers are wetted stably with acrylate at capillary numbers routinely exceeding 1000. It is hypothesized that this is possible because of dissolution of air into the liquid coating. A lubrication/boundary integral analysis that includes gas diffusion and solubility is developed. It is applied using conservatively estimated solubility and diffusivity coefficients and solutions are found that are consistent with industry practice and with the hypothesis. The results also agree with the claim of Deneka, Kar & Mensah (1988) that the use of high solubility gases to bathe a wetting line allows significantly greater wetting speeds. The solutions indicate a maximum speed of wetting which increases with gas solubility and with reduction in wetting-channel diameter.

Jacqmin, David↗

Recovery of resources for advanced life support space applications: effect of retention time on biodegradation of two crop residues in a fed-batch, continuous stirred tank reactor

Bioreactor retention time is a key process variable that will influence costs that are relevant to long distance space travel or long duration space habitation. However. little is known about the effects of this parameter on the microbiological treatment options that are being proposed for Advanced Life Support (ALS) systems. Two bioreactor studies were designed to examine this variable. In the first one, six retention times ranging from 1.3 to 21.3 days--were run in duplicate, 81 working-volume continuous stirred tank reactors (CSTR) that were fed ALS wheat residues. Ash-free dry weight loss, carbon mineralization, soluble TOC reduction, changes in fiber content (cellulose, hemicellulose, and lignin), bacterial numbers, and mineral recoveries were monitored. At short retention times--1.33 days--biodegradation was poor (total: 16-20%, cellulose - 12%, hemicellulose - 28%) but soluble TOC was decreased by 75-80% and recovery of major crop inorganic nutrients was adequate, except for phosphorus. A high proportion of the total bacteria (ca. 83%) was actively respiring. At the longest retention time tested, 21.3 days, biodegradation was good (total: 55-60%, cellulose ca. 70%, hemicellulose - ca. 55%) and soluble TOC was decreased by 80%. Recovery of major nutrients, except phosphorus, remained adequate. A very low proportion of total bacteria was actively respiring (ca. 16%). The second bioreactor study used potato residue to determine if even shorter retention times could be used (range 0.25-2.0 days). Although overall biodegradation deteriorated, the degradation of soluble TOC continued to be ca. 75%. We conclude that if the goal of ALS bioprocessing is maximal degradation of crop residues, including cellulose, then retention times of 10 days or longer will be needed. If the goal is to provide inorganic nutrients with the smallest volume/weight bioreactor possible, then a retention time of 1 day (or less) is sufficient.

Non-NASA Center↗