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At least 91 records · Page 5

A Novel Unitized Regenerative Proton Exchange Membrane Fuel Cell

A difficulty encountered in designing a unitized regenerative proton exchange membrane (PEM) fuel cell lies in the incompatibility of electrode structures and electrocatalyst materials optimized for either of the two functions (fuel cell or electrolyzer) with the needs of the other function. This difficulty is compounded in previous regenerative fuel cell designs by the fact that water, which is needed for proton conduction in the PEM during both modes of operation, is the reactant supplied to the anode in the electrolyzer mode of operation and the product formed at the cathode in the fuel cell mode. Drawbacks associated with existing regenerative fuel cells have been addressed. In a first innovation, electrodes function either as oxidation electrodes (hydrogen ionization or oxygen evolution) or as reduction electrodes (oxygen reduction or hydrogen evolution) in the fuel cell and electrolyzer modes, respectively. Control of liquid water within the regenerative fuel cell has been brought about by a second innovation. A novel PEM has been developed with internal channels that permit the direct access of water along the length of the membrane. Lateral diffusion of water along the polymer chains of the PEM provides the water needed at electrode/PEM interfaces. Fabrication of the novel single cell unitized regenerative fuel cell and results obtained on testing it are presented.

Murphy, O. J.↗

Elucidation of the Cross-Link Structure of Nadic-End-Capped Polyimides Using NMR of C-13-Labeled Polymers

Solid NMR of C-13 isotope-labeled samples of PMR-15 was used to follow the cross-linking reaction of the nadic end cap. Some samples were labeled on one of the carbon atoms of the nadic end cap, and others on the methylene carbon atom of the methylenedianiline portion of the polymer. NMR spectra were run on these samples both before and after cross-linking. In this way, direct evidence of the major products of cross-linking under normal cure conditions is provided. The majority (approximately 85%) of the cross-linking derives from olefin polymerization through the double bond of the end cap. Approximately 15% of the products could come from a pathway involving a retro-Diels-Alder reaction. However, all of the products could be explained by a biradical intermediate without a retro-Diels-Alder reaction. Evidence is also presented that the methylene moiety in the methylenedianiline part of the polymer chain also participates in the cross-linking, albeit to a small extent, by a radical transfer reaction. Different cure conditions (higher temperatures, longer times) could change the relative distribution of the products.

Meador, Mary Ann B.↗

Synthesis and Characterization of a Chitosan Derivative for Electro-Optical Applications

Chitin is a naturally occurring polymer of alpha(1-4) poly N-acetylglucosamine found primarily in the shells of crustaceans and insects. This polymer is chemically and thermally stable and physically durable as a consequence of hydrogen bonding which causes the alignment and ordering of the polymer chains into microcrystals which aggregate into sheets with chiral nematic order. Industry has attempted to take advantage of chitin's properties and low cost (chitin is a waste product of the shellfish industry) to produce durable fibers and other products. This has been largely unsuccessful because of chitin's non reactivity and insolubility. Chitosan is the deacetylation product of chitin and retains many of the structural properties of chitin. Unlike chitin, chitosan is soluble in aqueous solution at reduced pH making it easier to be processed into fibers and films than chitin. Chitosan and its derivatives are now used in such commercial applications as wound dressings, waste water treatment, and in pharmaceuticals. In this study, we have synthesized a chitosan derivative, N-para-nitrophenyl chitosan (NPNPC), as a model material with potential applications in electro optics.

Prastofer, Thomas↗

Effect of X-Rays on the Mechanical Properties of Aluminized FEP Teflon(R)

Pieces of the multilayer insulation (MLI) that is integral to the thermal control of the Hubble Space Telescope (HST) have been returned by two servicing missions after 3.6 and 6.8 years in orbit. They reveal that the outer layer, which is made from 5 mil (0.13 mm)thick aluminized fluorinated ethylene propylene(FEP) Teflon(R), has become severely embrittled. Although possible agents of this embrittlement include electromagnetic radiation across the entire solar spectrum, trapped particle radiation, atomic oxygen, and thermal cycling, intensive investigations have not yielded unambiguous causes. Previous studies utilizing monoenergetic photons in the 69-1900 eV range did not cause significant embrittlement, even at much higher doses than were experienced by the HST MLI. Neither did x-rays in the 3 to 10 keV range generated in a modified electron beam evaporator. An antidotal aluminized FEP sample that was exposed to an intensive dose from unfiltered Mo x-ray radiation from a rotating anode generator, however, did show the requisite embrittlement. Thus, a study was undertaken to determine the effects of x-ray exposure on the embrittlement of aluminized FEP in hopes that it might elucidate the HST MLI degradation mechanism. Tensile specimens of aluminized 5 mil thick FEP were exposed to a constant fluence of unfiltered x-ray radiation from a Mo target whose maximum energy ranged from 20-60 kV. Other samples were annealed, thermally cycled (100x) between 77-333 K, or cycled and irradiated. Tensile tests and density measurements were then performed on the samples. Only the samples which had been irradiated had the drastically reduced elongation-to-break, characteristic of the HST samples. Thermal cycling may accelerate the embrittlement, but the effect was near the scatter in the measurements. Annealing and thermal cycling had no apparent effect. Only the samples which had been irradiated and annealed showed significant density increases, likely implicating polymer chain scission and annealing.

Gaier, James R.↗

Effect of X-Rays on the Mechanical Properties of Aluminized FEP Teflon(trademark)

Pieces of the multilayer insulation (MLI) that is integral to the thermal control of the Hubble Space Telescope (HST) have been returned by two servicing missions after 3.6 and 6.8 years in orbit. They reveal that the outer layer, which is made from 5 mil (0.13 mm) thick aluminized fluorinated ethylenepropylene (FEP) Teflon. has become severely embrittled. Although possible agents of this embrittlement include electromagnetic radiation across the entire solar spectrum, trapped particle radiation, atomic oxygen, and thermal cycling, intensive investigations have not yielded unambiguous causes. Previous studies utilizing monoenergetic photons in the 69-1900 eV range did not cause significant embrittlement, even at much higher doses than were experienced by the HST MLI. Neither did x-rays in the 3 to 10 keV range generated in a modified electron bean evaporator. An antidotal aluminized FEP sample that was exposed to an intensive dose from unfiltered Mo x-ray radiation from a rotating anode generator, however, did show the requisite embrittlement. Thus, a study was undertaken to determine the effects of x-ray exposure on the embrittlement of aluminized FEP in hopes that it might elucidate the HST MLI degradation mechanism. Tensile specimens of aluminized 5 mil thick FEP were exposed to a constant fluence of unfiltered x-ray radiation from a Mo target whose maximum energy ranged from 20-60 kV. Other samples were annealed, thermally cycled (100x) between 77-333 K, or cycled and irradiated. Tensile tests and density measurements were then performed on the samples. Only the samples which had been irradiated had the drastically reduced elongation-to-break, characteristic of the HST samples. Thermal cycling may accelerate the embrittlement, but the effect was near the scatter in the measurements. Annealing and thermal cycling had no apparent effect. Only the samples which had been irradiated and annealed showed significant density increases, likely implicating polymer chain scission and annealing.

Gaier, James R.↗

Oxidative Degradation of Nadic-End-Capped Polyimides: Evidence for Reactions Occurring at High Temperatures - 2

The oxidative degradation of PMR (for polymerization of monomeric reactants) polyimides at elevated temperatures was followed by cross-polarized magic angle spinning (Cp-MAS) NMR. C-13 labeling of selected sites in the polymers allowed for direct observation of the transformations arising from oxidation processes. As opposed to model compound studies, the reactions were followed directly in the polymer. The labeling experiments confirm the previously reported oxidation of the methylene carbon to ketone in the methylenedianiline portion of the polymer chain. They also show the formation of two other oxidized species, acid and ester, from this same carbon. In addition, the technique provides the first evidence of the kind of degradation reactions that are occurring in the nadic end caps. Several PMR formulations containing moieties determined to be present after oxidation, as suggested by the labeling study, were synthesized. Weight loss, FTIR, and natural abundance NMR of these derivatives were followed during aging. In this way, weight loss could be related to the observed transformations.

Meador, Mary Ann B.↗

Flow-induced birefringence measurement system using dual-crystal transverse electro-optic modulator for microgravity fluid physics applications

We have developed a new instrument that can measure fast transient birefringence and polymer chain orientation angle in complex fluids. The instrument uses a dual-crystal transverse electro-optic modulator with the second crystal's modulation voltage applied 180 deg out of phase from that of the first crystal. In this manner, the second crystal compensates for the intrinsic static birefringence of the first crystal, and it doubles the modulation depth. By incorporating a transverse electro-optic modulator with two lithium-niobate (LiNbO3) crystals oriented orthogonal to each other with a custom-designed optical system, we have produced a very small robust instrument capable of fast transient retardation measurements. By measuring the sample thickness or optical path length through the sample, we can calculate the transient birefringence. This system can also measure dichroism. We have compared the calibration results and retardation and orientation angle measurements of this instrument with those of a photoelastic modulator (PEM) based system using a quarter wave plate and a high-precision 1/16-wave plate to simulate a birefringent sample. Transient birefringence measurements on the order of 10(exp -9) can be measured using either modulator.

Mackey, Jeffrey R.↗

Thermal Expansion and Diffusion Coefficients of Carbon Nanotube-Polymer Composites

Classical molecular dynamics (MD) simulations employing Brenner potential for intra-nanotube interactions and van der Waals forces for polymer-nanotube interface have been used to investigate thermal expansion and diffusion characteristics of carbon nanotube-polyethylene composites. Addition of carbon nanotubes to polymer matrix is found to significantly increase the glass transition temperature Tg, and thermal expansion and diffusion coefficients in the composite above Tg. The increase has been attributed to the temperature dependent increase of the excluded volume for the polymer chains, and the findings could have implications in the composite processing, coating and painting applications.

Wei, Chengyu↗

Adhesive Properties of Cured Phenylethynyl Containing Imides

Considerable attention has been directed towards acetylene terminated oligomers over the last 20 years' and recent work has focused on phenylethynyl terminated imide (PETI) oligomers. These reactive oligomers possess several features which make them attractive candidates for use as composite matrices and adhesives. The phenylethynyl group can be readily incorporated into many different functionalized oligomers. The reactive oligomers possess relatively low melt viscosities and thermally cure without the evolution of volatile by-products. Once cured, they typically display high glass transition temperatures (Tgs), excellent solvent resistance and high mechanical properties. new modified phenylethynyl-terminated imide (LaRC MPEI) oligomers were synthesized at various molecular weights utilizing a small amount of trifunctional amine. As long as the amount of triamine is relatively small, this approach produces a mixture of linear, star-shaped and branched polymer chains that has lower melt and solution viscosity than an equivalent molecular weight linear phenylethynyl terminated imide oligomers. The work reported herein involves the synthesis and characterization of a copolymer using this approach and the preparation of blends utilizing a phenylethynyl containing reactive plasticizer of lower molecular weight called LaRC LV-121. The chemistry and properties of this new MPEI as well as some blends of MPEI with LV-121, are presented and compared to the linear version, LARC-PETI-5.

Jensen, Brian J.↗

Field Effect Transistor Behavior in Electrospun Polyaniline/Polyethylene Oxide Nanofibers

Novel transistors and logic devices based on nanotechnology concepts are under intense development. The potential for ultra-low-power circuitry makes nanotechnology attractive for applications such as digital electronics and sensors. For NASA applications, nanotechnology offers tremendous opportunities for increased onboard data processing, and thus autonomous decision-making ability, and novel sensors that detect and respond to environmental stimuli with little oversight requirements. Polyaniline (PANi) is an intriguing material because its electrical conductivity can be changed from insulating to metallic by varying the doping levels and conformations of the polymer chain, and when combined with polyethylene oxide (PEO), can be formed into nanofibers with diameters ranging from approximately 50 to 500 nm (depending on the deposition conditions). The initial goal of this work was to demonstrate transistor behavior in these nanofibers, thus creating a foundation for future logic devices.

Miranda, Felix A.↗

Coating for gasifiable carbon-graphite fibers

A thin, uniform, firmly adherent coating of metal gasification catalyst is applied to a carbon-graphite fiber by first coating the fiber with a film-forming polymer containing functional moieties capable of reaction with the catalytic metal ions. Multivalent metal cations such as calcium cross-link the polymer such as a polyacrylic acid to insolubilize the film by forming catalytic metal macro-salt links between adjacent polymer chains. The coated fibers are used as reinforcement for resin composites and will gasify upon combustion without evolving conductive airborne fragments.

Harper-Tervet, Jan↗

Internal stabilization of polycarbonate resins by two stage radiation process

A new polycarbonate copolymer resin is formed by internal generation of stabilizers bound to the polymer chain. Irradiation of a solid piece or a deoxygenated solution of the resin at a first frequency below 300 nm generates 2 to 8 mol percent of phenyl salicylate groups which are rearranged to dihydroxybenzophenone groups by irradiating the resin under oxygen excluding conditions at a second frequency from 300 to 320 nm.

Gupta, Amitava↗

Fluorinated monomers useful for preparing fluorinated polyquinoline polymers

A new class of polymers is provided, as well as the monomers used for their preparation. The polymers provided in accordance with practice of the present invention include repeating units comprising one or more quinoline groups, wherein at least a portion of the repeating units includes a hexafluoroisopropylidene (6F) group or a 1-aryl-2,2,2-trifluoroethylidene (3F) group, or both. The hexafluoroisopropylidene group is referred to herein as a 6F group and has the following structure: ##STR1## The 6F group includes a tetravalent carbon atom bound to two trifluoromethyl moieties, with its other two bonds forming linkages in the polymer chain. The 1-aryl-2,2,2-trifluoroethylidene group is referred to herein as a 3F group and has the following structure: ##STR2## wherein Ar' is an aryl group.

Hendricks, Neil H.↗

Highly porous and mechanically strong ceramic oxide aerogels

Structurally stable and mechanically strong ceramic oxide aerogels are provided. The aerogels are cross-linked via organic polymer chains that are attached to and extend from surface-bound functional groups provided or present over the internal surfaces of a mesoporous ceramic oxide particle network via appropriate chemical reactions. The functional groups can be hydroxyl groups, which are native to ceramic oxides, or they can be non-hydroxyl functional groups that can be decorated over the internal surfaces of the ceramic oxide network. Methods of preparing such mechanically strong ceramic oxide aerogels also are provided.

Leventis, Nicholas↗

Developing Flexible, High Performance Polymers with Self-Healing Capabilities

Flexible, high performance polymers such as polyimides are often employed in aerospace applications. They typically find uses in areas where improved physical characteristics such as fire resistance, long term thermal stability, and solvent resistance are required. It is anticipated that such polymers could find uses in future long duration exploration missions as well. Their use would be even more advantageous if self-healing capability or mechanisms could be incorporated into these polymers. Such innovative approaches are currently being studied at the NASA Kennedy Space Center for use in high performance wiring systems or inflatable and habitation structures. Self-healing or self-sealing capability would significantly reduce maintenance requirements, and increase the safety and reliability performance of the systems into which these polymers would be incorporated. Many unique challenges need to be overcome in order to incorporate a self-healing mechanism into flexible, high performance polymers. Significant research into the incorporation of a self-healing mechanism into structural composites has been carried out over the past decade by a number of groups, notable among them being the University of I1linois [I]. Various mechanisms for the introduction of self-healing have been investigated. Examples of these are: 1) Microcapsule-based healant delivery. 2) Vascular network delivery. 3) Damage induced triggering of latent substrate properties. Successful self-healing has been demonstrated in structural epoxy systems with almost complete reestablishment of composite strength being achieved through the use of microcapsulation technology. However, the incorporation of a self-healing mechanism into a system in which the material is flexible, or a thin film, is much more challenging. In the case of using microencapsulation, healant core content must be small enough to reside in films less than 0.1 millimeters thick, and must overcome significant capillary and surface tension forces to flow, mix and react to achieve healing. Vascular networks small enough to fit into such films must also overcome these same flow limitations. Self-healing has also been demonstrated in ionomeric substrates such as Surlyn , wherein the heat generated by a projectile impact triggers the latent ability of this substrate to flow back to its original shape. Recent work using Diels-Alder reactions have shown promise in bringing about actual reforming of broken chemical bonds to achieve self-healing [2]. All self-healing mechanisms that rely on the use of inherent latent substrate properties require some degree of polymer chain flow to achieve any significant level of healing.

Jolley, Scott T.↗

Highly porous and mechanically strong ceramic oxide aerogels

Structurally stable and mechanically strong ceramic oxide aerogels are provided. The aerogels are cross-linked via organic polymer chains that are attached to and extend from surface-bound functional groups provided or present over the internal surfaces of a mesoporous ceramic oxide particle network via appropriate chemical reactions. The functional groups can be hydroxyl groups, which are native to ceramic oxides, or they can be non-hydroxyl functional groups that can be decorated over the internal surfaces of the ceramic oxide network. Methods of preparing such mechanically strong ceramic oxide aerogels also are provided.

Leventis, Nicholas↗

Highly porous ceramic oxide aerogels having improved flexibility

Ceramic oxide aerogels having improved flexibility are disclosed. Preferred embodiments exhibit high modulus and other strength properties despite their improved flexibility. The gels may be polymer cross-linked via organic polymer chains to further improve strength properties, without substantially detracting from the improved flexibility. Methods of making such aerogels are also disclosed.

Meador, Mary Ann B.↗

Highly porous ceramic oxide aerogels having improved flexibility

Ceramic oxide aerogels incorporating periodically dispersed flexible linkages are provided. The flexible linkages impart greater flexibility than the native aerogels without those linkages, and have been shown to reduce or eliminate the need for supercritical CO.sub.2-mediated drying of the corresponding wet gels. The gels may also be polymer cross-linked via organic polymer chains that are attached to and extend from surface-bound functional groups provided or present over the internal surfaces of a mesoporous ceramic oxide particle network via appropriate chemical reactions.

Meador, Mary Ann B.↗