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NASA NTRS1987

Correlation of Catalytic Rates With Solubility Parameters

Catalyst maximizes activity when its solubility parameter equals that of reactive species. Catalytic activities of some binary metal alloys at maximum when alloy compositions correspond to Hildebrand solubility parameters equal to those of reactive atomic species on catalyst. If this suggestive correlation proves to be general, applied to formulation of other mixed-metal catalysts. Also used to identify reactive species in certain catalytic reactions.

Lawson, Daniel D.↗

NASA NTRS1987

Adhesive evaluation of water-soluble LARC-TPI

The water-soluble polyimide, identified as TPI(MTC)/H2O, was evaluated as a high temperature thermoplastic adhesive for bonding Ti-6Al-4V and comparing those results primarily with results reported in earlier work with the polyamic-acid/diglyme material. The lap shear strength test was the primary test performed to evaluate the adhesive before (controls) and after thermal exposure in air at 204 C for up to 5000 hours and after a 72 hour water-boil exposure. Lap shear strengths were determined at RT, 177, 204, and 232 C. The adhesive was also characterized after fracture by determining the glass transition temperature as well as defining the mode of failure by visual observation. In general, the results indicate that the TPI(MTC)/H2O retains high lap shear strengths after thermal exposure but had reduced strengths after the water-boil exposure. All failures were cohesive. The TPI(MTC)/H2O compared very well with previous data reported for the standard polyamic-acid/diglyme LARC-TPI results, and therefore, shows promise as a water-soluble adhesive for use in various applications.

Progar, Donald J.↗

NASA NTRS1987

Synthesis and solution imidization studies of soluble poly(imide siloxane) segmented copolymers

Soluble metalinked poly(imide siloxane) segmented copolymers were synthesized utilizing a THF/NMP cosolvent system. The presence of dual solvent makes it possibled to reach high molecular weight in the amid acid stage. Incorporation of siloxanes at about 10 weight percent or higher enables the materials to be fully soluble in a range of polar solvents even after imidization. Imidization may be achieved either by conventional thermal methods on cast amic acid films or in appropriate solvent/azeotroping-agent systems employing moderate temperatures. The imidization procedure has been followed by FT-IR and NMR studies. FT-IR studies show the solution imidization follows first order kinetics and proceeds to about 96 percent completion. NMR studies of the isolated products show residual amic acid may be present after solution imidization, but only at very low levels. Properties of the solution imidized materials compared well with those obtained from samples imidized as thin films.

Summers, J. D.↗

NASA NTRS1988

Adhesive evaluation of water-soluble LARC-TPI

Progar, D. J.↗

NASA NTRS1989

Characterization of a thermally imidized soluble polyimide film

A soluble aromatic poly(amic acid) film was converted to a soluble polyimide by staging at 25 deg intervals to 325 C and characterized at each interval by several analytical methods. The behavior observed was consistent with an interpretation that a reduction occurred in molecular weight of the poly(amic acid) during the initial stages of cure before the ultimate molecular weight was achieved as a polyimide. This interpretation was supported by the results of solution viscosity, gel permeation chromatography, low angle laser light scattering photometry and infrared spectroscopy analysis. The results serve to increase the fundamental understanding of how polyimides are thermally formed from poly(amic acids).

Young, Philip R.↗

NASA NTRS1990

Hydrogen permeation, diffusion and solubility in IN-100 and Waspaloy

An attempt has been made to determine the permeation rate of hydrogen in IN-100 and Waspaloy by determining the evolution rate of hydrogen from a closed capsule of the test materials. Enclosed vanadium hydride was the source of hydrogen in the capsule. The presentation discusses the treatment of data and assesses the validity of the techniques in permeation measurement. In addition to permeation experiments, the solubility and diffusion of hydrogen in IN-100 and Waspaloy were also determined. For hydrogen diffusion in Waspaloy, Delta H was 38.5 kJ and D(0) was 0.0026 sq cm/sec. For IN-100, Delta H was 68.2 kJ and D(0) was 0.059 sq cm /sec. Both IN-100 and Waspaloy exhibited limited solubility of hydrogen at pressures up to 340 atmospheres hydrogen.

Khan, A. S.↗

NASA NTRS1990

Characterization of a thermally imidized soluble polyimide film

Young, Philip R.↗

NASA NTRS1992

Experimental determination of the solubility of iridium in silicate melts: Preliminary results

Little is known of the geochemical behavior of iridium. Normally this element is taken to be chalcophile and/or siderophile so that during planetary differentiation processes, e.g., core formation, iridium is extracted from silicate phases into metallic phases. Experimental determination of the metal/silicate partition coefficient of iridium is difficult simply because it is so large. Also there are no data on the solubility behavior of iridium in silicate melts. With information on the solubility of iridium in silicate melts it is possible, in combination with experimental data for Fe-Ir alloys, to calculate the partition coefficient between a metallic phase and a silicate melt.

Borisov, Alexander↗

NASA NTRS1992

The effect of oxygen fugacity on the solubility of carbon-oxygen fluids in basaltic melt

The solubility of CO2-CO fluids in a midocean ridge basalt have been measured at 1200 C, 500-1500 bar, and oxygen fugacities between NNO and NNO-4. In agreement with results of previous studies, the results reported here imply that, at least at low pressures, CO2 dissolves in basaltic melt only in the form of carbonate groups. The dissolution reaction is heterogeneous, with CO2 molecules in the fluid reacting directly with reactive oxygens in the melt to produce CO3(2-). CO, on the other hand, is insoluble, dissolving neither as carbon, molecular CO, nor CO3(2-). It is shown that, for a given pressure and temperature, the concentration of dissolved carbon-bearing species in basaltic melt in equilibrium with a carbon-oxygen fluid is proportional to the mole fraction of CO2 in the fluid, which is a function of fO2. At low pressures CO2 solubility is a linear function of CO2 fugacity at constant temperatures.

Pawley, Alison R.↗

NASA NTRS1993

A process for preparing an assembly of an article and a soluble polyimide which resists dimensional change, delamination, and debonding when exposed to changes in temperature

An assembly of an article and a polyimide is prepared. The assembly resists dimensional change, delamination, or debonding when exposed to changes in temperature. An article is provided. A soluble polyimide resin solution having a low coefficient of thermal expansion (CTE) was prepared by dissolving the polyimide in solvent and adding a metal ion-containing additive to the solution. Examples of the additive are: Ho(OOCCH3), Er(NPPA)3, TmCl3, and Er(C5H7O2)3. The soluble polyimide resin is combined with the article to form the assembly.

Stoakley, Diane M.↗

NASA NTRS1993

Temperature dependence of protein solubility-determination, application to crystallization, and growth kinetics studies

A scintillation method was developed for determinations of the temperature dependence of the solubility, and of nucleation induction times of proteins, in 50-100 mu(l) volumes of solution. Solubility data for lysozyme and horse serum albumin were obtained for various combinations of pH and precipitant concentrations. These data and the nucleation induction information were used for dynamic crystallization control, that is, for the controlled separation of nucleation and growth stages. Individual lysozyme and horse serum albumin crystals were grown in 15-20 mu(l) solution volumes contained in x-ray capillaries. The morphology and kinetics of the growth and dissolution of lysozyme in aqueous solutions with 2.5 percent NaCl and at pH = 4.5 was studied in situ with a depth resolution of 300 A (4 unit cells) by high resolution optical microscopy and digital image processing. The bulk super- or under saturation, sigma, of the solution inside a closed growth cell was controlled by temperature. The growth habit was bound by (110) and (101) faces that grew through layer spreading, although with different growth rate dependencies on supersaturation/temperature. At sigma less than 10 (obtained at higher temperatures) growth was purely kinetic ally controlled, with impurity effects (macrostep formation and kinetic hindrance) becoming significant for sigma less than 2. At sigma greater than 10 (lower temperatures), anisotropies in the interfacial kinetics were more pronounced, with interfacial kinetics and bulk transport becoming equally important to the growth morphology. Growth rates were growth history dependent. The formation of striations (layers of irregularly incorporated solution) was unambiguously correlated with growth temperature variations. Etching exposed dislocations and various high-index faces whose growth morphologies were studied during return to the steady state growth form. Growth steps were observed to originate from two-dimensional nuclei or from outcrops of growth striations, and from dislocations that preferentially formed in growth sector boundaries.

Rosenberger, Franz↗

NASA NTRS1994

Tough, soluble, aromatic, thermoplastic copolyimides

Tough, soluble, aromatic, thermoplastic copolyimides were prepared by reacting 4,4'-oxydiphthalic anhydride, 3,4,3',4'-biphenyltetracarboxylic dianhydride and 3,4'-oxydianiline. These copolyimides were found to be soluble in common amide solvents such as acetamide, Nmethylpyrrolidinone, and dimethylformamide allowing them to be applied as the fully imidized copolymer and to be used to prepare a wide range of articles.

Bryant, Robert G.↗

NASA NTRS1996

Asian Influence Over the Western North Pacific during the Fall Season: Inferences from Lead 210, Soluble Ionic Species and Ozone

Aerosol samples collected over the western Pacific during the NASA/Global Tropospheric Experiment Pacific Exploratory Mission (PEM-West A) expedition (September - October 1991) revealed mean Pb-210 concentrations in the free troposphere in the 5-10 fCi m(exp -3) STP range. Most soluble ionic aerosol-associated species were near detection limits [much less than 40 parts per trillion by volume (pptv)] in these same samples. The altitude distribution of O3 near Asia closely resembled that of Pb-210, while no relationship was found between the concentrations of O3 and Be-7. Free tropospheric air over the western Pacific was depleted in soluble aerosol-associated species but enriched in Pb-210 and O3, indicative of deep wet convection over the Asian continent. The influence of Asian air on the composition of the free troposphere over the western Pacific was evident on most of the PEM-West A flights. However, evidence of continental influence was largely restricted to those species that are relatively insoluble (or have insoluble precursors), hence escape scavenging during vertical transport from the boundary layer into the free troposphere by wet convective activity.

Dibb, J. E.↗

NASA NTRS1998

Tough, Soluble, Aromatic, Thermoplastic Copolyimides

Tough, soluble, aromatic, thermoplastic copolyimides were prepared by reacting 4,4'-oxydiphthalic anhydride, 3,4,3',4'-biphenyltetracarboxylic dianhydride and 3,4'-oxydianiline. These copolyimides were found to be soluble in common amide solvents such as N,N'-dimethyl acetamide, N-methylpyrrolidinone, and dimethylformamide allowing them to be applied as the fully imidized copolymer and to be used to prepare a wide range of articles.

Bryant, Robert G.↗

NASA NTRS2001

Detection of Soluble and Fixed NH4+ in Clay Minerals by DTA and IR Reflectance Spectroscopy : A Potential Tool for Planetary Surface Exploration

Nitrogen is an essential element for life. It is the only element among the six major biogenic elements, C, O, S, O, P, H, whose presence in the Martian soil has not been positively and directly established. We describe here a study assessing the ability to detect NH4 in soils by two methods: differential thermal analysis (DTA) and infrared (IR) reflectance spectroscopy. Four standard clay minerals (kaolinite, montmorillonite, illite and attapulgite) and an altered tephra sample from Mauna Kea were treated with NH4 in this study. Samples of the NH4-treated and leached clays were analyzed by DTA and infrared (IR) reflectance spectroscopy to quantify the delectability of soluble and sorbed/fixed NH4. An exotherm at 270-280 C was clearly detected in the DTA curves of NH4-treated (non-leached) samples. This feature is assigned to the thermal decomposition reaction of NH4. Spectral bands observed at 1.56, 2.05, 2.12, 3.06, 3.3, 3.5, 5.7 and 7.0 microns in the reflectance spectra of NH4-treated and leached samples are assigned to the sorbed/fixed ammonium in the clays. The montmorillonite has shown the most intense absorbance due to fixed ammonium among the leached samples in this study, as a result of its high cation sorption capacity. It is concluded that the presence of sorbed or fixed NH4 in clays may be detected by infrared (IR) reflectance or emission spectroscopy. Distinction between soluble and sorbed NH4 may be achieved through the presence or absence of several spectral features assigned to the sorbed NH4 moietyi and, specifically, by use of the 4.2 micrometer feature assigned to solution NH4. Thermal analyses furnish supporting evidence of ammonia in our study through detection of N released at temperatures of 270-330 C. Based on these results it is estimated that IR spectra measured from a rover should be able to detect ammonia if present above 20 mg NH4/g sample in the surface layers. Orbital IR spectra and thermal analyses measured on a rover may be able to detect ammonia in soils as well but at higher abundances. The spectral features at 3.06 and 7.0 microns due to bound NH4 in clays and altered Hawaiian tephra appear to be the most promising for detection by orbital spectrometers. If N species are present on Mars the sedimentary deposits may be the best regions to look for them.

Janice, Bishop↗

NASA NTRS2001

Solubility of methanol in low-temperature aqueous sulfuric acid and implications for atmospheric particle composition

Using traditional Knudsen cell techniques, we find well-behaved Henry's law uptake of methanol in aqueous 45 - 70 wt% H2SO4 solutions at temperatures between 197 and 231 K. Solubility of methanol increases with decreasing temperature and increasing acidity, with an effective Henry's law coefficient ranging from 10(exp 5) - 10(exp 8) M/atm. Equilibrium uptake of methanol into sulfuric acid aerosol particles in the upper troposphere and lower stratosphere will not appreciably alter gas-phase concentrations of methanol. The observed room temperature reaction between methanol and sulfuric acid is too slow to provide a sink for gaseous methanol at the temperatures of the upper troposphere and lower stratosphere. It is also too slow to produce sufficient quantities of soluble reaction products to explain the large amount of unidentified organic material seen in particles of the upper troposphere.

Iraci, Laura T.↗

NASA NTRS1996

Carbon Isotope Fractionations Associated with Methanotrophic Growth with the Soluble and Particulate Methane Monooxygenases

Growth experiments with the RuMP-type methanotroph, Methylococcus capsulatus (Bath), have demonstrated that biomass and lipid biomarkers are significantly depleted in C-13 compared to the substrate methane and that the extent of fractionation is dependent on whether cells express the soluble (s) or particulate (p) methane monooxygenase (MMO). The presence or absence of the characteristic sMMO subunits was monitored using SDS-polyacrylamide gels. In M. capsulatus grown with no Cu supplementation, the characteristic sMMO subunits were observed in the soluble fraction throughout the entire growth period and biomass was depleted in C-13 by approximately 14,700 relative to substrate methane. In cells grown with 5uM Cu, no sMMO bands were observed and a greater fractionation of approximately 27,700 in resultant biomass was obtained. Methanol growth experiments with M. capsulatus and with a RuMP methylotroph, Methylophilus methylotrophus, in which biomass measurements yielded depletions in C-13 of 9 and 5%(sub o), respectively, suggest that oxidation of methane is the major fractionation step. Growth of M. capsulatus at a low level of oxygen, approximately 0.5%, had no significant effect on carbon isotope fractionation by either sMMO or pMMO. These observations are significant for identification of molecular biomarkers; and methanotrophic contributions to carbon isotope composition in natural environments.

Jahnke, Linda L.↗

NASA NTRS2005

Detection of a Water Soluble Component of the Tagish Lake Meteorite

The Tagish Lake meteorite is a highly carbonaceous meteorite, with a carbon content of approximately 5% by weight [1]. Its composition and mineralogy suggest it lies between a CI1 and CM2 chondrite [2]. Part of the meteorite [the pristine fraction] was collected from the ice on Tagish Lake within one week of its landfall on Jan. 18, 2000 and this sample is considered to be the most pristine meteorite samples collected to date with regard to organic terrestrial contamination. It has been reported that only 100 ppm of the organic matter in the Tagish Lake meteorite is water soluble [3]. greater absorbance in the sigma bonding region between 290-300 eV suggesting that the soluble material contains more CH/CH2/CH3 bonds than the microtomed piece.

Wirick, S.↗