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At least 181 records · Page 10

New Aptes Cross-linked Polymers from Poly(ethylene oxide)s and Cyanuric Chloride for Lithium Batteries

A new series of polymer electrolytes for use as membranes for lithium batteries are described. Electrolytes were made by polymerization between cyanuric chloride and diamino-terminated poly(ethylene oxide)s, followed by cross-linking via a sol-gel process. Thermal analysis and lithium conductivity of freestanding polymer films were studied. The effects of several variables on conductivity were investigated, such as length of backbone PEO chain, length of branching PEO chain, extent of branching, extent of cross-linking, salt content, and salt counterion. Polymer films with the highest percentage of PEO were found to be the most conductive, with a maximum lithium conductivity of 3.9 x 10(exp -5) S/cm at 25 C. Addition of plasticizer to the dry polymers increased conductivity by an order of magnitude.

Tigelaar, Dean M.↗

Thermal rearrangements of unsaturated polymers

Thermal anaerobic uncatalyzed cyclizations and cis-trans isomerizations observed in unsaturated hydrocarbon polymers are surveyed. Three main types of cyclizations are described. Type I is a radical reaction which is caused by chain rupture and gives rise to six-membered rings; this reaction occurs during pyrolysis of polymers with double bonds in a 1,5- or 1,6-diene configuration. Type II is a (2 + 2) thermal cycloaddition of double bonds in certain polymers with a 1,6-diene structure; bicycloheptane structures result. Type III is an intramolecular ene reaction. Many polymers containing a double bond linking CH units display thermal cis-trans isomerization. The common activation energy is approximately 130 kJ/mol, and the initial rate constants are lower, for homologous polymers, the greater the separation of the carbon-carbon double bonds.

Golub, M. A.↗

Cure study of soluble aromatic polyimide films

Several soluble aromatic poly(amic acid) films were staged at intervals to 325 C and characterized by IR spectroscopy and various solution property techniques. A series of films in which the polymer had been endcapped in an effort to control chain extension was also examined. Much of the behavior observed is consistent with an interpretation that a reduction in molecular weight occurred during cure before the ultimate molecular weight was achieved as a polyimide.

Young, Philip R.↗

Initial adhesive screening of novel polyamide-imides and their copolymers

Continued interest by the research community in thermally stable, tough, high temperature adhesives has resulted in the investigation by Langley Research Center of two linear aromatic polyamide-imide (PAI) homopolymers and two linear aromatic PAI copolymers. The homopolymers were made with either 3,3'=DABA or 4,4'-DABA and BTDA. The two polymers were prepared with a monomer ratio of 0.75 DABP:0.25 DABA:1.00 BTDA. These aromatic PAIs possess high thermal stability because of intermolecular hydrogen bonding and chain stiffness. Lap shear strength (LSS) was the main criteria used to evaluate the polymers as adhesives. LSS of bonded Ti-6Al-4V was determined at room temperature (RT), 177, 204 and 232 C. The glass transition temperature and the type of bond failure were also determined. The best LSS values of the four adhesive systems investigated were obtained with the PAI copolymer identified in the report as LARC-TPI (25 percent 3,3'-DABA); however, it did not produce LSSs nearly as high as LARC-TPI. The poor flow properties observed appear to be due to a combination of high molecular weight and the increased interchain electronic interactions associated with the amide group.

Donald J Progar↗

Initial evaluation of novel polyamide-imides and their copolymers as adhesives

Continued interest by the research community in thermally stable, tough, high temperature adhesives has resulted in the investigation by Langley Research Center of two linear aromatic polyamide-imide (PAI) homopolymers and two linear aromatic PAI copolymers. The homopolymers were made with either 3,3'=DABA or 4,4'-DABA and BTDA. The two polymers were prepared with a monomer ratio of 0.75 DABP:0.25 DABA:1.00 BTDA. These aromatic PAIs possess high thermal stability because of intermolecular hydrogen bonding and chain stiffness. Lap shear strength (LSS) was the main criteria used to evaluate the polymers as adhesives. LSS of bonded Ti-6Al-4V was determined at room temperature (RT), 177, 204 and 232 C. The glass transition temperature and the type of bond failure were also determined. The best LSS values of the four adhesive systems investigated were obtained with the PAI copolymer identified in the report as LARC-TPI (25 percent 3,3'-DABA); however, it did not produce LSSs nearly as high as LARC-TPI. The poor flow properties observed appear to be due to a combination of high molecular weight and the increased interchain electronic interactions associated with the amide group.

Progar, Donald J.↗

Synthesis and Characterization of Polymers for Fuel Cells Application

The goal of this summer research is to prepare Polymer Exchange Membranes (PEM s) for fuel cell application. Several high temperature polymers such as polybenzimidazoles and polyether ketones were known to possess good high temperature stability and had been investigated by post-sulfonation to yield sulfonated polymers. The research project will involve two approaches: 1. Synthesis of polybenzimidazoles and then react with alkyl sultonse to attach an aliphatic sulfonic groups. 2. Synthesis of monomers containing sulfonic acid units either on a aromatic ring or on an aliphatic chain and then polymerize the monomers to form high molecular weight sulfonate polymers.

Tytko, Stephen F.↗

Open cell fire-resistant foam

Candidate polyphosphazene polymers were investigated to develop a fire-resistant, thermally stable and flexible open cell foam. The copolymers were prepared in several mole ratios of the substituent side chains and a (nominal) 40:60 derivative was selected for formulation studies. Synthesis of the polymers involved solution by polymerization of hexachlorophosphazene to soluble high molecular weight poly(dichlorophosphazene), followed by derivatization of the resultant polymer in a normal fashion to give polymers in high yield and high molecular weight. Small amounts of a cure site were incorporated into the polymer for vulcanization purposes. The poly(aryloxyphosphazenes) exhibited good thermal stability and the first polymer mentioned above exhibited the best thermal behavior of all the candidate polymers studied.

Thompson, J. E.↗

Elastomer Reinforced with Carbon Nanotubes

Elastomers are reinforced with functionalized, single-walled carbon nanotubes (SWNTs) giving them high-breaking strain levels and low densities. Cross-linked elastomers are prepared using amine-terminated, poly(dimethylsiloxane) (PDMS), with an average molecular weight of 5,000 daltons, and a functionalized SWNT. Cross-link densities, estimated on the basis of swelling data in toluene (a dispersing solvent) indicated that the polymer underwent cross-linking at the ends of the chains. This thermally initiated cross-linking was found to occur only in the presence of the aryl alcohol functionalized SWNTs. The cross-link could have been via a hydrogen-bonding mechanism between the amine and the free hydroxyl group, or via attack of the amine on the ester linage to form an amide. Tensile properties examined at room temperature indicate a three-fold increase in the tensile modulus of the elastomer, with rupture and failure of the elastomer occurring at a strain of 6.5.

Hudson, Jared L.↗

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.↗

Plastic deformation mechanisms in polyimide resins and their semi-interpenetrating networks

High-performance thermoset resins and composites are critical to the future growth of space, aircraft, and defense industries in the USA. However, the processing-structure-property relationships in these materials remain poorly understood. In the present ASEE/NASA Summer Research Program, the plastic deformation modes and toughening mechanisms in single-phase and multiphase thermoset resins were investigated. Both thermoplastic and thermoset polyimide resins and their interpenetrating networks (IPNs and semi-IPNs) were included. The fundamental tendency to undergo strain localization (crazing and shear banding) as opposed to a more diffuse (or homogeneous) deformation in these polymers were evaluated. Other possible toughening mechanisms in multiphase thermoset resins were also examined. The topological features of network chain configuration/conformation and the multiplicity of phase morphology in INPs and semi-IPNs provide unprecedented opportunities for studying the toughening mechanisms in multiphase thermoset polymers and their fiber composites.

Jang, Bor Z.↗

Low-Melt Polyamic Acid Based Powder Coatings

The present invention is directed to a method for powder coating a metal substrate using a low-melt polyamic acid (PAA) polymer that readily imidizes to polyimides. These low-melt PAAs have been shown to be useful in resins applied as powder coatings to metal surfaces. The resin includes an end-capping material capable of providing crosslinking functionality to at least one end of the low-melt PAA polymer. The end-capping material functions dually as a polymerization chain terminator and crosslinking agent, thus producing resins that have molecular weights low enough to flow well and form good cured films applicable for use in powder coating.

Jolley, Scott T.↗

Space Applications of Polymeric Materials

Polymers constitute an extremely large class of materials generally based on carbon chemistry. Their long chain structures and unique molecular architecture make them distinct from metals and ceramics and provided them with a very wide range of properties.

Polymer Outgassing radiation composites inflatable↗

Polymer-gas reactions (air pollutants: NO2 and SO2) as function of pressure, UV light, temperature, and morphology: A survey

Reactions of various polymers, such as polystyrene and its stereo-specific isomers, butylrubber, nylon, etc., with nitrogen dioxide and sulfur-dioxide were studied over the past few years. More recently, work has been initiated on the influence of polymer morphology on degradation of polymers in presence of these gases, near UV radiation and oxygen. Unexpected effects have been observed during chain scission near room temperature. Thus, for instance, isotactic polystyrene of various crystallinities, as far as extent and type are concerned, show marked differences in their degradation characteristics. Thus, for instance, crystalline polymers show faster degradation than amorphous ones, which seems to be contrary to expectations. However, this phenomenon can be explained in quite a consistent manner. The importance of all these reactions in connection with air pollution is briefly discussed.

Jellinek, H. H. G.↗

Process for synthesizing and formulating condensed ring polymers

Chemical process for forming low molecular weight, fully cyclized heteroaromatic prepolymers under conditions which limit chain extension or branching is described. Exact procedures used in conducting chemical reaction are defined. Advantages of process over conventional methods are presented.

Hughes, C. T.↗

REACTER: A Heuristic Method for Reactive Molecular Dynamics

REACTER (www.reacter.org) is a heuristic protocol that enables the simulation of complex reactions using atomistic molecular dynamics (MD) with a fixed-valence force field. Incorporating reactions into classical MD with this approach allows modeling of reactive systems over greatly-increased time scales, enabling systems to be modeled with MD that would not otherwise be feasible. One or more competing multi-step reactions or series of reactions can be invoked simultaneously. Special treatment can be applied to neighboring atoms to relax high energy configurations while the simulation progresses. The original version of REACTER, which was implemented in the open-source LAMMPS simulation package as fix bond/react, was only available for serial simulations. This work describes the expansion of fix bond/react for use in parallel simulations, as well as the addition of various new options, including deletion of reaction by-products, reversible reactions, and custom reaction constraints. These new capabilities are demonstrated through large-scale simulations (200,000+ atoms) of the polymerization of polystyrene and nylon 6,6. The morphologies of both polymers are analyzed after reaching >99% extent of polymerization. Finally, the newly-added reversible reactions feature is demonstrated by rupturing these highly-entangled systems under uniaxial strain by defining a chain scission reaction.

polymer simulations, molecular dynamics↗

Induced anisotropy of thermal conductivity of polymer solids under large strains

A simple analytical form of induced anisotropy of heat conductivity of initially isotropic polymer solids results from employing the simplified theory of the three-chain model of the non-Gaussian network. The analytical form appears to be valid up to a stretch ratio of 2.65, which is the limit of existing experimental data. The effect of induced anisotropy on the temperature distribution, due to the large deformations, is illustrated for a highly expanded spherical shell and a cylindrical tube under a steady-state heat flow using the derived analytical form of the strain-dependent heat conductivity.

Peng, S. T. J.↗

Deuteron NMR (Nuclear Magnetic Resonance) in relation to the glass transition in polymers

H-2NMR is introduced as a tool for investigating slow molecular motion in the glass transition region of amorphous polymers. In particular, we compare H-2 spin alignment echo spectra of chain deuterated polystyrene with model calculations for restricted rotational Brownian motion. Molecular motion in the polyztyrene-toluene system has been investigated by analyzing H-2NMR of partially deuterated polystyrene and toluene, respectively. The diluent mobility in the mixed glass has been decomposed into solid and liquid components where the respective average correlation times differ by more than 5 decades.

Roessler, E.↗