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At least 181 records · Page 10

Structure-property study of keto-ether polyimides

As part of an on-going effort to develop an understanding of how changes in the chemical structure affect polymer properties, an empirical study was performed on polyimides containing only ether and/or carbonyl connecting groups in the polymer backbone. During the past two decades the structure-property relationships in linear aromatic polyimides have been extensively investigated. More recently, work has been performed to study the effect of isomeric attachment of keto-ether polyimides on properties such as glass transition temperature and solubility. However, little work has been reported on the relation of polyimide structure to mechanical properties. The purpose of this study was to determine the effect of structural changes in the backbone of keto-ether polyimides on their mechanical properties, specifically, unoriented thin film tensile properties. This study was conducted in two stages. The purpose of the initial stage was to examine the physical and mechanical properties of a representative group (four) of polyimide systems to determine the optimum solvent and cure cycle requirements. These optimum conditions were then utilized in the second stage to prepare films of keto-ether polyimides which were evaluated for mechanical and physical properties. All of the polyimides were prepared using isomers of oxydianiline (ODA) and diaminobenzophenone (DABP) in combination with 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) and 4,4'-oxydiphthalic anhydride (ODPA).

Dezern, James F.↗

Polybenzimidazoles Via Aromatic Nucleophilic Displacement

Novel molecular weight controlled and endcapped polybenzimidazoles (PBI) are prepared by the aromatic nucleophilic displacement reaction of di(hydroxyphenylbenzimidazole) monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The PBI are endcapped with mono(hydroxyphenyl)benzimidazoles. The polymerizations are carried out in polar aprotic solvents such as N-methyl-2-pyrrolidinone or N,N-dimethylacetamide using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. Mono(hydroxyphenyl)benzimidazoles are synthesized by reacting phenyl-4-hydroxybenzoate with aromatic (o-diamine)s in diphenylsulfone. Molecular weight controlled and endcapped PBI of new chemical structures are prepared that exhibit a favorable combination of physical and mechanical properties.

Connell, John W.↗

Effect of osteoblastic culture conditions on the structure of poly(DL-lactic-co-glycolic acid) foam scaffolds

Poly(DL-lactic-co-glycolic acid) (PLGA) foams are an osteoconductive support that holds promise for the development of bone tissue in vitro and implantation into orthopedic defects. Because it is desirable that foams maintain their shape and size, we examined a variety of foams cultured in vitro with osteoblastic cells. Foams were prepared with different porosities and pore sizes by the method of solvent casting/porogen leaching using 80, 85, and 90 wt% NaCl sieved with particle sizes of 150-300 and 300-500 microm and characterized by mercury intrusion porosimetry. Foams seeded with cells were found to have volumes after 7 days in static culture that decreased with increasing porosity: the least porous exhibited no change in volume while the most porous foams decreased by 39 +/- 10%. In addition, a correlation was observed between decreasing foam volume after 7 days in culture and decreasing internal surface area of the foams prior to seeding. Furthermore, foams prepared with the 300-500 microm porogen had lower porosities, greater mean wall thicknesses between adjacent pores, and larger volumes after 7 days in culture than those prepared with the smaller porogen. Two culture conditions for maintaining cells, static and agitated (in a rotary vessel), were found to have similar influences on foam size, cell density, and osteoblastic function for 7 and 14 days in culture. Finally, we examined unseeded foams in aqueous solutions of pH 3.0, 5.0, and 7.4 and found no significant decrease in foam size with degradation. This study demonstrates that adherent osteoblastic cells may collapse very porous PLGA foams prepared by solvent casting/particulate leaching: a potentially undesirable property for repair of orthopedic defects.

NASA Program Fundamental Space Biology↗

Determination of the thermal stability of perfluoropolyalkyl ethers by tensimetry

The thermal decomposition temperatures of several perfluoropolyalkyl ether fluids were determined with a computerized tensimeter. In general, the decomposition temperatures of the commercial fluids were all similar and significantly higher than those for noncommercial fluids. Correlation of the decomposition temperatures with the molecular structures of the primary components of the commercial fluids revealed that the stability of the fluids was not affected by carbon chain length, branching, or adjacent difluoroformal groups. Instead, stability was limited by the presence of small quantities of thermally unstable material and/or chlorine-containing material arising from the use of chlorine containing solvents during synthesis. Finally, correlation of decomposition temperatures with molecular weights for two fluids supports a chain cleavage reaction mechanism for one and an unzipping reaction mechanism for the other.

Helmick, Larry A.↗

Poly(N-arylenbenzimidazoles) via aromatic nucleophilic displacement

Novel poly(N-arylenebenzimidazole)s (PNABIs) are prepared by the aromatic nucleophilic displacement reaction of novel di(hydroxyphenyl-N-arylene benzimidazole) monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The polymerizations are carried out in polar aprotic solvents such as N-methyl-2-pyrrolidinone or N,N-dimethylacetamide using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. The di(hydroxyphenyl N-arylenebenzimidazole) monomers are synthesized by reacting phenyl 4-hydroxybenzoate with bis(2-aminoanilino) arylenes in diphenylsulfone. Moderate molecular weight PNABIs of new chemical structures were prepared that exhibit a favorable combination of physical and mechanical properties. The use of the novel di(hydroxyphenyl N-arylenebenzimidazole)s permits a more economical and easier way to prepare PNABIs than previous routes.

Connell, John W.↗

Poly(N-arylenebenzimidazole)s via aromatic nucleophilic displacement

Novel poly(N-arylenebenzimidazole)s (PNABls) are prepared by the aromatic nucleophilic displacement reaction of novel di(hydroxyphenyl-N-arylene benzimidazole) monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The polymerizations are carried out in polar aprotic solvents such as N-methyl-2-pyrrolidinone or N,N-dimethylacetamide using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. The di(hydroxyphenyl-N-arylenebenzimidazole) monomers are synthesized by reacting phenyl-4-hydroxybenzoate with bis(2-aminoanilino)arylenes in diphenylsulfone. Moderate molecular weight PNABIs of new chemical structures were prepared that exhibit a favorable combination of physical and mechanical properties. The use of the novel di(hydroxyphenyI-N-arylenebenzimidazole)s permits a more economical and easier way to prepare PNABIs than previous routes.

Connell, John W.↗

Soluble and colorless polyimides

Results are reported in the form of reaction diagrams, graphs, and tables of research being conducted to synthesize and characterize linear aromatic polyimides which are soluble in common organic solvents and optically transparent in the 400-600 nm spectral range. These flexible and high-temperature polymeric films and coatings are needed for specific applications on space components such as antennas, solar cells, and thermal control coating systems. Several series of these polyimide films have been produced by making variations in the polymer molecular structure aimed at reducing the electronic interactions between the polymer chains.

St. Clair, Anne K.↗

Methods of Attaching or Grafting Carbon Nanotubes to Silicon Surfaces and Composite Structures Derived Therefrom

The present invention is directed toward methods of attaching or grafting carbon nanotubes (CNTs) to silicon surfaces. In some embodiments, such attaching or grafting occurs via functional groups on either or both of the CNTs and silicon surface. In some embodiments, the methods of the present invention include: (1) reacting a silicon surface with a functionalizing agent (such as oligo(phenylene ethynylene)) to form a functionalized silicon surface; (2) dispersing a quantity of CNTs in a solvent to form dispersed CNTs; and (3) reacting the functionalized silicon surface with the dispersed CNTs. The present invention is also directed to the novel compositions produced by such methods.

Tour, James M.↗

Electrochemical Cell for Obtaining Oxygen from Carbon Dioxide Atmospheres

To support human life on the Martian surface, an electrochemical device will be required to obtain oxygen from the carbon dioxide rich atmosphere. The electrolyte employed in such a device must be constructed from extremely thin, dense membranes to efficiently acquire the oxygen necessary to support life. A forming process used industrially in the production of multilayer capacitors and electronic substrates was adapted to form the thin membranes required. The process, known as the tape casting, involves the suspension consisting of solvents and binders. The suspension is passed under a blade, resulting in the production of ceramic membranes between 0.1 and 0.5 mm thick. Once fired, the stabilized zirconia membranes were assembled into the cell design by employing a zirconium phosphate solution as the sealing agent. The resulting ceramic-to-ceramic seals were found to be structurally sound and gas-tight. Furthermore, by using a zirconia-based solution to assemble the cell, the problem of a thermal expansion mismatch was alleviated. By adopting an industrial forming process to produce thin membranes, an electrochemical cell for obtaining oxygen from carbon dioxide was produced. The proposed cell design is unique in that it does not require a complicated manifold system for separating the various gases present in this process, nor does it require a series of complex electrical connections. Thus, the device can reliably obtain the vital oxygen supply from the toxic carbon dioxide atmosphere.

Hooker, Matthew↗

The Wettability of LaRC Colorless Polyimide Resins on Casting Surfaces

Two colorless polyimides developed at NASA Langley Research Center, LaRC -CP1 and LaRC -CP2, are noted for being optically transparent, resistant to radiation, and soluble in the imide form. These materials may be used to make transparent, thin polymer films for building large space reflector/collector inflatable antennas, solar arrays, radiometers, etc. Structures such as these require large area, seamless films produced via spin casting or spray coating the soluble imide on a variety of substrates. The ability of the soluble imide to wet and spread over the mandrel or casting substrate is needed information for processing these structures with minimum waste and reprocessing, thereby, reducing the production costs. The wettability of a liquid is reported as the contact angle of the solid/liquid system. This fairly simple measurement is complicated by the porosity and the amount of contamination of the solid substrate. This work investigates the effect of inherent viscosity, concentration of polyimide solids, and solvent type on the wettability of various curing surfaces.

Miner, Gilda A.↗

Composite Electrolytes for Lithium Batteries: Ionic Liquids in APTES Crosslinked Polymers

Solvent free polymer electrolytes were made consisting of Li(+) and pyrrolidinium salts of trifluoromethanesulfonimide added to a series of hyperbranched poly(ethylene oxide)s (PEO). The polymers were connected by triazine linkages and crosslinked by a sol-gel process to provide mechanical strength. The connecting PEO groups were varied to help understand the effects of polymer structure on electrolyte conductivity in the presence of ionic liquids. Polymers were also made that contain poly(dimethylsiloxane) groups, which provide increased flexibility without interacting with lithium ions. When large amounts of ionic liquid are added, there is little dependence of conductivity on the polymer structure. However, when smaller amounts of ionic liquid are added, the inherent conductivity of the polymer becomes a factor. These electrolytes are more conductive than those made with high molecular weight PEO imbibed with ionic liquids at ambient temperatures, due to the amorphous nature of the polymer.

Tigelaar, Dean M.↗

Synthesis and Properties of Cross-Linked Polyamide Aerogels

We report the first synthesis of cross-linked polyamide aerogels through step growth polymerization using a combination of diamines, diacid chloride and triacid chloride. Polyamide oligomers endcapped with amines are prepared as stable solutions in N-methylpyrrolidinone from several different diamine precursors and 1,3-benzenedicarbonyl dichloride. Addition of 1,3,5-benzenetricarbonyl trichloride yields gels which form in under five minutes according to the scheme shown. Solvent exchange of the gels into ethanol, followed by drying using supercritical CO2 extraction gives colorless aerogels with densities around 0.1 to 0.2 gcm3. Thicker monolithes of the polyamide aerogels are stiff and strong, while thin films of certain formulations are highly flexible, durable, and even translucent. These materials may have use as insulation for deployable space structures, rovers, habitats or extravehicular activity suits as well as in many terrestrial applications. Strucure property relationships of the aerogels, including surface area, mechanical properties, and thermal conductivity will be discussed.

Aerogel↗

Macroscopic and bulk-controlled elastic modes in an interaction of interstitial alcali metal cations within a face-centered cubic crystalline fullerine

The calculations in a majority of previous works for the fulleride (AqC-60) crystals were performed within the framework of the rigid-lattice model, neglecting the distortion relaxation of the host fullerene (C-60) crystal caused by the interstitial alkali-metal (A) cations. However, an each cation is a source of a static distortion field, and the resulting field is a superposition of such fields generated by all cations. This is a reason why the host-crystal distortions depend on the A-cations configurations, i.e. on a type of a spatial bulk distribution of interstitial cations. The given paper seeks to find a functional relation between the amplitudes of the doping-induced structure-distortion waves and of static concentration ones. A semiphenomenological model is constructed here within the scope of statistical-thermodynamic treatment and using the lattice-statistics simulation method(*). In this model the effects due to the presence of q solute A cations over available interstices (per unit cell) on the static inherent reorientation and/or displacements of the solvent molecules from the 'average-lattice' sites' as well as on the lattice parameter a of a elastically-anysotropic 'cubic' C-60 crystal are taken into account.

Tatarenko, Valentine A.↗

Method to Prepare Processable Polyimides with Non-Reactive Endgroups Using 1,3-bis(3-Aminophenoxy) Benzene

Polyimide copolymers were obtained containing 1,3-bis(3-aminophenoxy)benzene (APB) and other diamines and dianhydrides and terminating with the appropriate amount of a non-reactive endcapper, such as phthalic anhydride. Homopolymers containing only other diamines and dianhydrides which are not processable under conditions described previously can be made processable by incorporating various amounts of APB, depending on the chemical structures of the diamines and dianhydrides used. Polyimides that are more rigid in nature require more APB to impart processability than polyimides that are less rigid in nature. The copolymers that result from using APB to enhance processability have a unique combination of properties including excellent thin film properties, low pressure processing (200 psi and below), improved toughness, improved solvent resistance, improved adhesive properties, improved composite mechanical properties, long term melt stability (several hours at 390 C), and lower melt viscosities.

Jensen, Brian J.↗

Developing Novel Fluorescent Materials with Near Infrared Emission by Using m-Phenylene

Our research focuses on development of novel p-conjugated polymers with desired emission. In the current study, the structure of a highly green-emitting poly[(m-phenylenevinylene)- alt-( p-phenylenevinylene)] has been modified by increasing the content of p-phenylene to achieve red- and infrared-emission. The polymer is synthesized via Wittig-Horner condensation, which is known to lead to trans-olefin linkage. The polymer is soluble in common organic solvents such as toluene, chloroform and THF. The spectroscopic properties of the polymer in both solution and film states will be discussed in comparison with its model compound.

Pang, Yi↗

The polymer-like organic material in the Orgueil meteorite

Results are reported for analysis of polymeric organic material contained in powder from the Orgueil chondrite, using a stepwise high-vacuum pyrolysis-gas chromatography-mass spectrometry technique. Pyrolysis products obtained include a series of alkanes and alkenes to C8, an extensive series of alkylbenzene isomers, thiophene, alkylthiophenes, benzothiophene, acetonitrile, acrylonitrile, benzonitrile, acetone, and phenol. Most of these products are shown to be similar both qualitatively and quantitatively to those previously obtained from solvent-extracted Allende powder, indicating a basically aromatic and heteroaromatic polymer matrix with short aliphatic bridges or side chains. The production of acrylonitrile, acetonitrile, and benzonitrile (common breakdown products of amino acids) from the insoluble organic material is taken to suggest that amino acids exist in an insoluble form, perhaps as peptides, in the meteorite's polymeric component. Similarities between the structure of the Orgueil polymeric material and terrestrial kerogen are discussed which raise the possibility that both might have been produced in part by similar reactions.

Bandurski, E. L.↗

Development of new and improved polymer matrix resin systems, phase 1

Vinystilbazole (vinylstryrylpyridine) and vinylpolystyrulpyridine were prepared for the purpose of modifying bismaleimide composite resins. Cure studies of resins systems were investigated by differential scanning calorimetry. The vinylstyrylpyridine-modified bismaleimide composite resins were found to have lower cure and gel temperatures, and shorter cure times than the corresponding unmodified composite resins. The resin systems were reinforced with commercially avialable satin-weave carbon cloth. Prepregs were fabricated by solvent or hot melt techniques. Thermal stability, flammability, moisture absorption, and mechanical properties of the composites (such as flexural strength, modulus, tensile and short beam shear strength) were determined. Composite laminates showed substantial improvements in both processability and mechanical properties compared to he bismaleimide control systems. The vinylstyrylpyridine modified bismaleimide resins can be used as advanced matrix resins for graphite secondary structures where ease of processing, fireworthiness, and high temperature stability are required for aerospace applications.

Hsu, M. S.↗

Evaluation of HCFC AK 225 Alternatives for Precision Cleaning and Verification

Maintaining qualified cleaning and verification processes are essential in an production environment. Environmental regulations have and are continuing to impact cleaning and verification processing in component and large structures, both at the Michoud Assembly Facility and component suppliers. The goal of the effort was to assure that the cleaning and verification proceeds unimpeded and that qualified, environmentally compliant material and process replacements are implemented and perform to specifications. The approach consisted of (1) selection of a Supersonic Gas-Liquid Cleaning System; (2) selection and evaluation of three cleaning and verification solvents as candidate alternatives to HCFC 225 (Vertrel 423 (HCFC), Vertrel MCA (HFC/1,2-Dichloroethylene), and HFE 7100DE (HFE/1,2 Dichloroethylene)); and evaluation of an analytical instrumental post cleaning verification technique. This document is presented in viewgraph format.

Melton, D. M.↗