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At least 91 records · Page 5

Micro and macro approaches to tough polymers for composites

The progress to date on the development of techniques to toughen continuous thermoplastic composites is summarized. The work, using the approach of toughening the polycarbonate composite matrix with rubber particles, has focused on determining the differences between Double Cantilever Beam (DCB) samples molded inhouse and those molded by NASA. Specifically, an effort was made to account for the differences in fracture toughness observed between the various specimens. In addition, preliminary results of tensile dilatometry tests are described; these tests suggest that processes leading to increased volume and enhanced shear banding are occurring within the rubber toughened system. The results of the effort using another approach, the preparation of random block copolycarbonates, are presented. The synthetic route to these species was modified so that higher molecular weights of these materials can be obtained. In addition, an attempt is being made to determine the exact block length or the number of functional groups in the oligomers since this procedure also should lead to high molecular weight materials. Dynamic mechanical analysis of the copolymer prepared so far indicates that the scale of cooperative molecular motion of the PBA polycarbonate at sub-Tg temperatures is larger than five monomer units. Efforts to find a suitable rubber-toughener for a thermoset system (bismaleimides) is also discussed. Included is a description of the various tougheners intended for use or currently being used.

Yee, Albert F.↗

Composite Solid Electrolyte Containing Li+- Conducting Fibers

Improved composite solid polymer electrolytes (CSPEs) are being developed for use in lithium-ion power cells. The matrix components of these composites, like those of some prior CSPEs, are high-molecular-weight dielectric polymers [generally based on polyethylene oxide (PEO)]. The filler components of these composites are continuous, highly-Li(+)-conductive, inorganic fibers. PEO-based polymers alone would be suitable for use as solid electrolytes, were it not for the fact that their room-temperature Li(+)-ion conductivities lie in the range between 10(exp -6) and 10(exp -8) S/cm, too low for practical applications. In a prior approach to formulating a CSPE, one utilizes nonconductive nanoscale inorganic filler particles to increase the interfacial stability of the conductive phase. The filler particles also trap some electrolyte impurities. The achievable increase in conductivity is limited by the nonconductive nature of the filler particles.

Appleby, A. John↗

Results of Simulated Galactic Cosmic Radiation (GCR) and Solar Particle Events (SPE) on Spectra Restraint Fabric

Spectra or similar Ultra-high-molecular-weight polyethylene (UHMWPE) fabric is the likely choice for future structural space suit restraint materials due to its high strength-to-weight ratio, abrasion resistance, and dimensional stability. During long duration space missions, space suits will be subjected to significant amounts of high-energy radiation from several different sources. To insure that pressure garment designs properly account for effects of radiation, it is important to characterize the mechanical changes to structural materials after they have been irradiated. White Sands Test Facility (WSFTF) collaborated with the Crew and Thermal Systems Division at the Johnson Space Center (JSC) to irradiate and test various space suit materials by examining their tensile properties through blunt probe puncture testing and single fiber tensile testing after the materials had been dosed at various levels of simulated GCR and SPE Iron and Proton beams at Brookhaven National Laboratories. The dosages were chosen based on a simulation developed by the Structural Engineering Division at JSC for the expected radiation dosages seen by space suit softgoods seen on a Mars reference mission. Spectra fabric tested in the effort saw equivalent dosages at 2x, 10x, and 20x the predicted dose as well as a simulated 50 year exposure to examine the range of effects on the material and examine whether any degradation due to GCR would be present if the suit softgoods were stored in deep space for a long period of time. This paper presents the results of this work and outlines the impact on space suit pressure garment design for long duration deep space missions.

Peters, Benjamin↗

Tri- and tetraterpenoid hydrocarbons in the Messel oil shale

The high-molecular-weight constituents of the branched and cyclic hydrocarbon fraction of the Messel oil shale (Eocene) have been examined by high-resolution gas chromatography and combined gas chromatography/mass spectrometry. The following compounds are present: perhydrolycopene, together with one or more unsaturated analogs with the same skeleton; a series of 4-methylsteranes in higher abundance than their 4-desmethyl analogs; two series of pentacyclic triterpanes, one series based on the hopane structure, and the other based on the 17 alpha-H hopane structure; and an intact triterpene hop-17(21)-ene. Only two additional triterpanes were detected in minor concentrations - namely, 30-normoretane and a C31 triterpane based on the hopane/lupane-type skeleton. The presence of these compounds suggests a significant microbial contribution to the forming sediment.

Kimble, B. J.↗

Carbon Isotopes of Alkanes in Hydrothermal Abiotic Organic Synthesis Processes at High Temperatures and Pressures: An Experimental Study

Observation of methane in the Martian atmosphere has been reported by different detection techniques [1-4]. With more evidence showing extensive water-rock interaction in Martian history [5-7], abiotic formation by Fischer-Tropsch Type (FTT) synthesis during serpentization reactions may be one possible process responsible for methane generation on Mars [8, 9]. While the experimental studies performed to date leave little doubt that chemical reactions exist for the abiotic synthesis of organic compounds by mineral surface-catalyzed reactions [10-12], little is known about the reaction pathways by which CO2 and/or CO are reduced under hydrothermal conditions. Carbon and hydrogen isotope measurements of alkanes have been used as an effective tool to constrain the origin and reaction pathways of hydrocarbon formation. Alkanes generated by thermal breakdown of high molecular weight organic compounds have carbon and hydrogen isotopic signatures completely distinct from those formed abiotically [13-15]. Recent experimental studies, however, showed that different abiogenic hydrocarbon formation processes (e.g., polymerization vs. depolymerization) may have different carbon and hydrogen isotopic patterns [16]. Results from previous experiments studying decomposition of higher molecular weight organic compounds (lignite) also suggested that pressure could be a crucial factor affecting fractionation of carbon isotopes [17]. Under high pressure conditions, no experimental data are available describing fractionation of carbon isotope during mineral catalyzed FTT synthesis. Thus, hydrothermal experiments present an excellent opportunity to provide the requisite carbon isotope data. Such data can also be used to identify reaction pathways of abiotic organic synthesis under experimental conditions.

Fu, Qi↗

Polyimides with improved compression moldability

The semicrystalline polyimide prepared by reaction of 3,3',4,4' benzophenonetetracarboxylic (BTDA) and 1,3-bis(4-aminophenoxy 4' benzoyl) benzene (1,3-BABB) is modified so that it can be more readily processed to form adhesive bonds, moldings, and composites. The stoichiometric ratio of the two monomers, BTDA and 1,3-BABB is controlled so that the intermediate polyamide acid is of a calculated molecular weight. A polyimide acid with excess anhydride groups is then reacted with the stoichiometrically required amount of monofunctional aromatic or aliphatic amine required for complete endcapping. The stoichiometrically offset, encapped polyimide is processed at lower temperatures and pressures than the unmodified high molecular weight polyimide with the same repeat unit, and exhibits an improved melt stability.

Hergenrother, Paul M.↗

Simulated dynamic response of a multi-stage compressor with variable molecular weight flow medium

A mathematical model of a multi-stage compressor with variable molecular weight flow medium is derived. The modeled system consists of a five stage, six cylinder, double acting, piston type compressor. Each stage is followed by a water cooled heat exchanger which serves to transfer the heat of compression from the gas. A high molecular weight gas (CFC-12) mixed with air in varying proportions is introduced to the suction of the compressor. Condensation of the heavy gas may occur in the upper stage heat exchangers. The state equations for the system are integrated using the Advanced Continuous Simulation Language (ACSL) for determining the system's dynamic and steady state characteristics under varying operating conditions.

Babcock, Dale A.↗

Synthesis of perfluoroalkylether triazine elastomers

A method of perfluoroalkylether triazine elastomer synthesis is described. To form an elastomer, the resultant polymer is heated in a closed oven at slightly reduced pressures for 1-day periods at 100, 130 and 150 C. A high-molecular-weight perfluoroalkylether triazine elastomer is produced that exhibits thermal and oxidative stability. This material is potentially useful in applications such as high-temperature seals, 'O' rings, and wire enamels.

Rosser, R. W.↗

Vinyl capped addition polyimides

Polyimide resins (PMR) are generally useful where high strength and temperature capabilities are required (at temperatures up to about 700 F). Polyimide resins are particularly useful in applications such as jet engine compressor components, for example, blades, vanes, air seals, air splitters, and engine casing parts. Aromatic vinyl capped addition polyimides are obtained by reacting a diamine, an ester of tetracarboxylic acid, and an aromatic vinyl compound. Low void materials with improved oxidative stability when exposed to 700 F air may be fabricated as fiber reinforced high molecular weight capped polyimide composites. The aromatic vinyl capped polyimides are provided with a more aromatic nature and are more thermally stable than highly aliphatic, norbornenyl-type end-capped polyimides employed in PMR resins. The substitution of aromatic vinyl end-caps for norbornenyl end-caps in addition polyimides results in polymers with improved oxidative stability.

Vannucci, Raymond D.↗

Liquid Crystalline Thermosets from Ester, Ester-Imide, and Ester-Amide Oligomers

Main chain thermotropic liquid crystal esters, ester-imides, and ester-amides were prepared from AA, BB, and AB type monomeric materials and were end-capped with phenylacetylene, phenylmaleimide, or nadimide reactive end-groups. The resulting reactive end-capped liquid crystal oligomers exhibit a variety of improved and preferred physical properties. The end-capped liquid crystal oligomers are thermotropic and have, preferably, molecular weights in the range of approximately 1000-15,OOO grams per mole. The end-capped liquid crystal oligomers have broad liquid crystalline melting ranges and exhibit high melt stability and very low melt viscosities at accessible temperatures. The end-capped liquid crystal oligomers are stable for up to an hour in the melt phase. These properties make the end-capped liquid crystal oligomers highly processable by a variety of melt process shape forming and blending techniques including film extrusion, fiber spinning, reactive injection molding (RIM), resin transfer molding (RTM), resin film injection (RFI), powder molding, pultrusion, injection molding, blow molding, plasma spraying and thermo-forming. Once processed and shaped, the end- capped liquid crystal oligomers were heated to further polymerize and form liquid crystalline thermosets (LCT). The fully cured products are rubbers above their glass transition temperatures. The resulting thermosets display many properties that are superior to their non-end-capped high molecular weight analogs.

Theodornus J Dingemans↗

Liquid crystalline thermosets from ester, ester-imide, and ester-amide oligomers

Main chain thermotropic liquid crystal esters, ester-imides, and ester-amides were prepared from AA, BB, and AB type monomeric materials and were end-capped with phenylacetylene, phenylmaleimide, or nadimide reactive end-groups. The resulting reactive end-capped liquid crystal oligomers exhibit a variety of improved and preferred physical properties. The end-capped liquid crystal oligomers are thermotropic and have, preferably, molecular weights in the range of approximately 1000-15,000 grams per mole. The end-capped liquid crystal oligomers have broad liquid crystalline melting ranges and exhibit high melt stability and very low melt viscosities at accessible temperatures. The end-capped liquid crystal oligomers are stable for up to an hour in the melt phase. These properties make the end-capped liquid crystal oligomers highly processable by a variety of melt process shape forming and blending techniques including film extrusion, fiber spinning, reactive injection molding (RIM), resin transfer molding (RTM), resin film injection (RFI), powder molding, pultrusion, injection molding, blow molding, plasma spraying and thermo-forming. Once processed and shaped, the end-capped liquid crystal oligomers were heated to further polymerize and form liquid crystalline thermosets (LCT). The fully cured products are rubbers above their glass transition temperatures. The resulting thermosets display many properties that are superior to their non-end-capped high molecular weight analogs.

Dingemans, Theodorous J.↗

Determinations of molecular weight and molecular weight distribution of high polymers by the rheological properties

Several methods are reviewed by which the molecular weight (MW) and the molecular weight distribution (MWD) of polymeric material were determined from the rheological properties. A poly(arylene ether) polymer with six different molecular weights was used in this investigation. Experimentally measured MW and MWD were conducted by GPC/LALLS (gel permeation chromatography/low angle laser light scattering), and the rheological properties of the melts were measured by a Rheometric System Four rheometer. It was found that qualitative information of the MW and MWD of these polymers could be derived from the viscoelastic properties, with the methods proposed by Zeichner and Patel, and by Dormier et al., by shifting the master curves of the dynamic storage modulus, G', and the loss modulus, G'', along the frequency axis. Efforts were also made to calculate quantitative profiles of MW and MWD for these polymers from their rheological properties. The technique recently proposed by Wu was evaluated. It was found that satisfactory results could only be obtained for polymers with single modal distribution in the molecular weight.

Huang, J. Y.↗

Poly/phenylquinoxalines/ containing ethynyl groups

The synthesis of high molecular weight linear poly(phenylquinoxalines) containing pendant ethynyl groups is reported, where thermally-induced reactions of the ethynyl groups provided insoluble, cross-linked polymers with high glass transition temperatures. The ethynyl-containing polymer exhibited fair to poor processability by compression molding due to the thermal reaction of the ethynyl groups, which inhibited polymer flow, depending on ethynyl density. This class of polymers is not expected to be useful as laminating resins or adhesives, due to the processing difficulties. Use for them may be found, however, as solvents and corrosion-resistant high-temperature coatings.

Hergenrother, P. M.↗

Ethynyl-terminated polyarylates - Synthesis and characterization

Hydroxy-terminated polyarylates (HTPA) with number-average molecular weights of approximately 2500, 5000, 7500, and 10,000 were synthesized and converted to corresponding 4-ethynylbenzoyloxy-terminated polyarylates (ETPA) by reaction with 4-ethynylbenzoyl chloride. The terminal ethynyl groups were thermally reacted to provide chain extension and crosslinking. The cured ETPA exhibited higher glass transition temperatures (Tg) and better solvent resistance than a high molecular weight linear polyarylate. Solvent resistance was further improved by curing 2,2-bis(4-ethynylbenzoyloxy-4-prime-phenyl) propane, a coreactant, with ETPA at concentrations of approximately 10 percent (w/w).

Havens, S. J.↗

Curable liquid hydrocarbon prepolymers containing hydroxyl groups and process for producing same

Production of hydroxyl containing curable liquid hydrocarbon prepolymers by ozonizing a high molecular weight saturated hydrocarbon polymer such as polyisobutylene or ethylene propylene rubber is discussed. The ozonized material is reduced using reducing agents, preferably diisobutyl aluminum hydride, to form the hydroxyl containing liquid prepolymers having a substantially lower molecular weight than the parent polymer. The resulting curable liquid hydroxyl containing prepolymers can be poured into a mold and readily cured, with reactants such as toluene diisocyanate, to produce highly stable elastomers having a variety of uses such as binders for solid propellants.

Rhein, R. A.↗

Red clouds in reducing atmospheres

A dark reddish-brown high-molecular weight polymer is produced by long wavelength ultraviolet irradiation of abundant gases in reducing planetary atmospheres. The polymer is examined by paper chromatography, mass spectrometry, and infrared, visible, and ultraviolet spectroscopy. High carbon-number straight-chain alkanes with NH2 and, probably, OH and C = O groups are identified, along with amino acids. There are chemical similarities between this polymer and organic compounds recovered from carbonaceous chondrites and precambrian sediments. The visible and near-ultraviolet transmission spectrum of the polymer shows its absorption optical depth to be redder than lambda(-2) and perhaps similar in coloration to the clouds of Jupiter, Saturn, and Titan. The nitrile content is small, and the polymer should be semitransparent in the 5 micrometer atmospheric window. Such polymers may be a common constituent of clouds in the outer solar system and on the early earth.

Khare, B. N.↗

Ultrahigh Molecular Weight Aromatic Siloxane Polymers

Silphenylene-siloxane polymers can be prepared by a condensation reaction of a diol 1,4-bis(hydroxydimethylsilyl)benzene and a silane bis(dimethylamino)dimethylsilane. Using a stepwise condensation technique, a polymer (R=CH3) with a molecular weight in excess of 1.0 x 1 million has been produced. The polymer exhibits increased thermal stability, compared to a methyl siloxane polymer without the aromatic phenyl ring in the backbone. The use of bis(dimethylamino)methylvinylsilane should allow for ready crosslinking at the vinyl sites (R=-CH=CH2) introduced into the backbone. However, under the conditions of the reaction system a high molecular weight polymer was not obtained or the polymer underwent a crosslinking process during the synthesis.

Ludwick, L. M.↗

Flame retardant polyphosphazenes

Three processes for the preparation of polyphosphazenes were investigated: (1) the reaction of bisphosphines with diazides, (2) the condensation of bisdichlorophosphoranes with diamines; and (3) the treatment of bisphosphines with diamines in the presence of carbon tetrachloride followed by base dehydrohalogenation. All products obtained were of low molecular weight; the degree of polymerization did not exceed twelve repeating units. However, several compositions exhibited good thermal stability. No weight loss was observed up to 390 C when heated in air at 5 C/min. Treatment of bisphosphines with either an excess of a diazide or an excess of a diamine in the presence of carbon tetrachloride resulted in the production of difunctional phosphazenes which were respectively, azido and amino terminated. The reaction of these azido terminated extended monomers with bisphosphines did not produce high molecular weight materials. The bis-aminophosphazene prepared for the first time under this contract was successfully incorporated into a polyimide.

Paciorek, K. L.↗