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At least 127 records · Page 7

FETs Based on Doped Polyaniline/Polyethylene Oxide Fibers

A family of experimental highly miniaturized field-effect transistors (FETs) is based on exploitation of the electrical properties of nanofibers of polyaniline/ polyethylene oxide (PANi/PEO) doped with camphorsulfonic acid. These polymer-based FETs have the potential for becoming building blocks of relatively inexpensive, low-voltage, highspeed logic circuits that could supplant complementary metal oxide/semiconductor (CMOS) logic circuits. The development of these polymerbased FETs offers advantages over the competing development of FETs based on carbon nanotubes. Whereas it is difficult to control the molecular structures and, hence, the electrical properties of carbon nanotubes, it is easy to tailor the electrical properties of these polymerbased FETs, throughout the range from insulating through semiconducting to metallic, through choices of doping levels and chemical manipulation of polymer side chains. A further advantage of doped PANi/PEO nanofibers is that they can be made to draw very small currents and operate at low voltage levels, and thus are promising for applications in which there are requirements to use many FETs to obtain large computational capabilities while minimizing power demands. Fabrication of an experimental FET in this family begins with the preparation of a substrate as follows: A layer of silicon dioxide between 50 and 200 nm thick is deposited on a highly doped (resistivity 0.01 W.cm) silicon substrate, then gold electrodes/contact stripes are deposited on the oxide. Next, one or more fibers of camphorsulphonic acid-doped PANi/PEO having diameters of the order of 100 nm are electrospun onto the substrate so as to span the gap between the gold electrodes (see Figure 1). Figure 2 depicts measured current-versus-voltage characteristics of the device of Figure 1, showing that saturation channel currents occur at source-todrain potentials that are surprisingly low, relative to those of CMOS FETs. The hole mobility in the depletion regime in this transistor was found to be 1.4 10(exp -4) sq cm/(V.s), while the one-dimensional charge density at zero gate bias was estimated to be approximately one hole per 50 two-ring repeat units of polyaniline, consistent with the rather high channel conductivity (approx. 10(exp -3) S/cm). Reducing or eliminating the PEO content of the fibers is expected to enhance the properties of future versions of this transistor.

Theofylaktos, Noulie↗

Improved Methods for Hyperelastic Material Characterizations Based on Uniaxial, Radial-Biaxial, and Strip-Biaxial Test Data

This report concerns the different analytical methods used for material characterizations of hyperelastic silicone rubber, a potential candidate elastomer for aerospace applications. To establish the constitutive equations for the silicon rubber, strain-energy gradients (material constants) must be determined from experiments. Earlier experiments by Blatz-Ko showed that the material constants of natural rubber determined from different stress fields were different. Therefore, in the current material characterization, uniaxial, equalbiaxial, and strip-biaxial tensile tests were conducted. Based on the resulting stress-stretch data, the material constants were determined by using a trendline on the stress-difference plots and energy plots, and also the MSC-Marc ® curve-fitting method. The results confirm that the material constants determined from uniaxial and biaxial stress fields are indeed different. The material constants determined from the equal-biaxial energy plots and from the MSC-Marc ® combined-curve-fitting method were found to be extremely close, and can be considered as universal material constants for establishing the constitutive equations for the silicone rubber under any stress field. The results of this report show that a uniaxially stretched specimen became slightly anisotropic due to crystallization of polymer molecular chains, and that equal-biaxial and strip-biaxial testing must be conducted to fully understand the material properties of hyperelastic materials.

William L Ko↗

Polymer composites containing nanotubes

The present invention relates to polymer composite materials containing carbon nanotubes, particularly to those containing singled-walled nanotubes. The invention provides a polymer composite comprising one or more base polymers, one or more functionalized m-phenylenevinylene-2,5-disubstituted-p-phenylenevinylene polymers and carbon nanotubes. The invention also relates to functionalized m-phenylenevinylene-2,5-disubstituted-p-phenylenevinylene polymers, particularly to m-phenylenevinylene-2,5-disubstituted-p-phenylenevinylene polymers having side chain functionalization, and more particularly to m-phenylenevinylene-2,5-disubstituted-p-phenylenevinylene polymers having olefin side chains and alkyl epoxy side chains. The invention further relates to methods of making polymer composites comprising carbon nanotubes.

Bley, Richard A.↗

Synthesis of Perfluorinated Polymers

Long-chain perfluoropolyethers containing functional pendent groups were investigated as possible candidates for new sealants and elastomers that function in extreme environments. Of specific interest was development of materials exhibiting high thermal and oxidative stability at temperatures around 400 degrees C, low-temperature flexibility with glass transition at about 50 degrees C, and hydrolytic stability as well as compatibility with metals and resistance to fuels.

Rosser, R. W.↗

Hexagonal and nematic phases of chains. I - Correlation functions. II - Phase transitions

The statistical mechanics of a system of semiflexible chains, which can represent polymer liquid crystals, long-chain biomolecules, stiff wormlike micelles, or columns of discotic liquid crystals, are examined. A continuum theory is used to calculate static correlation functions in the hexagonal and nematic phases. Two correlation functions are considered: (1) the structure factor which describes fluctuations in the density; and (2) the director fluctuation spectrum, which describes fluctuations in the local optical axis. In addition, a model is developed for the phase transitions of a system of infinitely long, semiflexible chains which interact through a steric, excluded-volume repulsion. The model yields generic phase diagrams in terms of pressure or density vs. persistence length or temperature.

Selinger, Jonathan V.↗

Flexible Polyimide Aerogels Derived From Use of Neopentyl Spacer in Backbone

Polyimide aerogels have gained much attention in the last decade due to their highly porous structure with low density, low dielectric constant, good mechanical properties and thermal stability. They are desirable for many aerospace and commercial applications including lightweight substrates for antennas for aerospace vehicles, due to the low dielectric constant, approaching one as density decreases. However, with only aromatic diamines in the backbone, the aerogels are flexible only as very thin films, nominally 0.5 mm thick. A more flexible aerogel substrate would allow them to be used as conformal antennas, which would reduce drag and also save space in aerospace vehicles. In this research, we demonstrate that the flexibility can be increased by substituting the aromatic diamines typically used in polyimide aerogels with 1,3-bis(4-aminophenoxy)-2, 2-dimethylpropane (BAPN), which contains a flexible neopentyl spacer group. Using the aliphatic diamine, BAPN, leads to aerogels with a high bend radius even when the aerogels are 2-3 mm thick. Twenty different formulations of polyimide aerogels were synthesized from 3,3’,4,4’-biphenyltetracarboxylic dianhydride (BPDA) and a combination of BAPN and 2,2’-dimethylbenxidine (DMBZ), and cross-linked with 1,3,5-triaminophenoxybenzene (TAB) to understand the effect of polymer concentration, oligomer chain length and concentration of BAPN on the properties of the aerogels. Aerogels made using 50 mol % BAPN with n of 45 and 7 wt % polymer possessed the best combination of properties conducive to use as a flexible substrate for conformal antennas, including low density, good hydrophobicity, low shrinkage with high surface area, a one-inch bend radius in aerogels up to 3 mm thickness, and a dielectric constant of 1.11.

polyimide aerogels↗

Viscoelastic cationic polymers containing the urethane linkage

A method for the synthesis and manufacturing of elastomeric compositions and articles containing quaternary nitrogen centers and condensation residues along the polymeric backbone of the centers is presented. Linear and cross-linked straight chain and block polymers having a wide damping temperature range were synthesized. Formulae for the viscoelastic cationic polymers are presented.

Rembaum, A.↗

Process for crosslinking and extending conjugated diene-containing polymers

A process using a Diels-Alder reaction which increases the molecular weight and/or crosslinks polymers by reacting the polymers with bisunsaturated dienophiles is developed. The polymer comprises at least 75% by weight based on the reaction product, has a molecular weight of at least 5000 and a plurality of conjugated 1,3-diene systems incorporated into the molecular structure. A dienophile reaction with the conjugated 1,3-diene of the polymer is at least 1% by weight based on the reaction product. Examples of the polymer include polyesters, polyamides, polyethers, polysulfones and copolymers. The bisunsaturated dienophiles may include bis-maleimides, bis maleic and bis tumaric esters and amides. This method for expanding the molecular weight chains of the polymers, preferable thermoplastics, is advantageous for processing or fabricating thermoplastics. A low molecular weight thermoplastic is converted to a high molecular weight plastic having improved strength and toughness for use in the completed end use article.

Bell, Vernon L.↗

Polyimide adhesives - Modified with ATBN and silicone elastomers

A series of studies evaluating the effects of added elastomers on the properties of a high-temperature addition polyimide adhesive is reviewed. First, thermoset polyimides containing various butadiene/acrylonitrile and silicone elastomers were synthesized either as physical polybends or by chemically reacting the elastomers directly onto the polymer backbone. The modified adhesive resins were characterized for thermomechanical properties, fracture toughness and adhesive strength. A second series of elastomer-containing polyimides was also prepared in order to study the effects of the elastomer chain length on polymer properties. Aromatic amine-terminated silicone rubbers with repeat units varying from n = 10 to 105 were reacted onto the polyimide backbone, and the resulting polymers were characterized for their adhesive properties.

St. Clair, A. K.↗

Titan haze: structure and properties of cyanoacetylene and cyanoacetylene-acetylene photopolymers

The structure and morphological properties of polymers produced photochemically from the UV irradiation of cyanoacetylene and cyanoacetylene mixtures have been examined to evaluate their possible contribution to the haze layers found on Titan. A structural analysis of these polymers may contribute to our understanding of the data returned from the Huygens probe of the Cassini mission that will pass through the atmosphere of Titan in the year 2004. Infrared analysis, elemental analysis, and thermal methods (thermogravimetric analysis, thermolysis, pyrolysis) were used to examine structures of polycyanoacetylenes produced by irradiation of the gas phase HC3N at 185 and 254 nm. The resulting brown to black polymer, which exists as small particles, is believed to be a branched chain of conjugated carbon-carbon double bonds, which, on exposure to heat, cyclizes to form a graphitic structure. Similar methods of analysis were used to show that when HC3N is photolyzed in the presence of Titan's other atmospheric constituents (CH4, C2H6, C2H2, and CO), a copolymer is formed in which the added gases are incorporated as substituents on the polymer chain. Of special significance is the copolymer of HC3N and acetylene (C2H2). Even in experiments where C2H2 was absorbing nearly all of the incident photons, the ratio of C2H2 to HC3N found in the resulting polymer was only 2:1. Scanning electron microscopy was used to visually examine the polymer particles. While pure polyacetylene particles are amorphous spheres roughly 1 micrometer in diameter, polycyanoacetylenes appear to be strands of rough, solid particles slightly smaller in size. The copolymer of HC3N and C2H2 exhibits characteristics of both pure polymers. This is particularly important as pure polyacetylenes do not match the optical constants measured for Titan's atmospheric hazes. The copolymers produced by the incorporation of other minor atmospheric constituents, like HC3N, into the polyacetylenes are expected to have optical constants more comparable to those of the Titan haze.

Non-NASA Center↗

Assembly of Colloidal Materials Using Bioadhesive Interactions

We have pursued the use of biological crosslinking molecules of several types to make colloidal materials at relatively low volume fraction of colloidal particles. The objective is to make binary alloys of colloidal particles, made of two different colloidal particles coated with complementary biological lock-and-key binding molecules, which assemble due to the biological specificity. The long-term goal is to use low affinity lock-and-key biological interactions, so that the can anneal to form crystalline states. We have used a variety of different surface chemistries in order to make colloidal materials. Our first system involved using selectin-carbohydrate (sialyl-Lewis) interactions; this chemistry is derived from immune system. This chemical interaction is of relatively low affinity, with timescales for dissociation of several seconds. Furthermore, the adhesion mediated by these molecules can be reversed by the chelation of calcium atoms; thus assembled structures can be disassembled reversibly. Our second system employed avidin-biotin chemistry. This well-studied system is of high affinity, and is generally irreversible on a laboratory time-scale. Thus, we would expect selectin-carbohydrate interactions at high molecular density and avidin-biotin interactions to give kinetically-trapped structures; however, at low densities, we would expect significant differences in the structure and dynamics of the two materials, owing to their very different release rates. We have also begun to use a third chemistry - DNA hybridization. By attaching single stranded DNA oligonucleotide chains to beads, we can drive the assembly of colloidal materials by hybridization of complementary DNA chains. It is well known that DNA adenosine-thymine (A-T) and guanine-cytosine (G-C) bases hybridize pairwise with a Gibbs free energy change of 1.7 kcal/mol per base; thus, the energy of the assembly can be modulated by altering the number of complementary bases in the DNA chains. Using these different crosslinking molecules, we have assembled colloidal materials from different-sized colloidal particles, A and B. In the first sets of experiment, we used high densities of adhesion molecules, and 0.96 micron (A) and 5.5 micron (B) diameter particles. The high density of adhesion molecules means that the structures are kinetically trapped in nonequilibrium configurations. The structure of the suspension can be varied by changing the number ratio of the two types of colloidal particles, NA and NB, where A is the smaller particle. With carbohydrate-selectin or avidin-biotin interactions, large NA/NB leads to the formation of colloidal micelles, with the large center B particle surrounded by many smaller A particles. As the ratio NA/NB decreases, the structures become more extended, approaching the formation of macro-Rouse polymers - extended linear chains where A beads are connected with intervening small B linkers.

Hammer, Daniel A.↗

The effect of elastomer chain length on properties of silicone-modified polyimide adhesives

A series of polyimides containing silicone elastomers was synthesized in order to study the effects of the elastomer chain length on polymer properties. The elastomer with repeat units varying from n=10 to 105 was chemically reacted into the backbone of an addition polyimide oligomer via reactive aromatic amine groups. Glass transition temperatures of the elastomer and polyimide phases were observed by torsional braid analysis. The elastomer-modified polyimides were tested as adhesives for bonding titanium in order to determine their potential for aerospace applications. Adhesive lap shear tests were performed before and after aging bonded specimens at elevated temperatures.

St.clair, A. K.↗

Challenges in Laser Sintering of Melt-Processable Thermoset Imide Resin

Polymer Laser Sintering (LS) is an additive manufacturing technique that builds 3D models layer by layer using a laser to selectively melt cross sections in powdered polymeric materials, following sequential slices of the CAD model. LS generally uses thermoplastic polymeric powders, such as polyamides (i.e. Nylon), and the resultant 3D objects are often weaker in their strength compared to traditionally processed materials, due to the lack of polymer inter-chain connection in the z-direction. The objective of this project is to investigate the possibility of printing a melt-processable RTM370 imide resin powder terminated with reactive phenylethynyl groups by LS, followed by a postcure in order to promote additional crosslinking to achieve higher temperature (250-300 C) capability. A preliminary study to build tensile specimens by LS and the corresponding DSC and rheology study of RTM370 during LS process is presented.

Additive Manufacturing↗

Challenges in Laser Sintering of Thermoset Imide Resin

Polymer Laser Sintering (LS) is an additive manufacturing technique that builds 3D models layer by layer using a laser to selectively melt cross sections in powdered polymeric materials, following sequential slices of the CAD model. LS generally uses thermoplastic polymeric powders, such as polyamides (i.e. Nylon), and the resultant 3D objects are often weaker in their strength compared to traditionally processed materials, due to the lack of polymer inter-chain connection in the z-direction. The objective of this project is to investigate the possibility of printing a melt-processable RTM370 imide resin powder terminated with reactive phenylethynyl groups by LS, followed by a postcure in order to promote additional crosslinking to achieve higher temperature (250-300 C) capability. A preliminary study to build tensile specimens by LS and the corresponding DSC and rheology study of RTM370 during LS process is presented.

Additive Manufacturing↗

Laser Sintering of Thermoset Polyimide Composites

Selective Laser Sintering (SLS) is an additive manufacturing technique that builds 3D models layer by layer using a laser to selectively melt cross sections in powdered polymeric materials, following sequential slices of the CAD model. SLS generally uses thermoplastic polymeric powders, such as polyamides (i.e. Nylon), and the resultant 3D objects are often weaker in their strength compared to traditionally processed materials, due to the lack of polymer inter-chain connection in the z-direction. Our previous effort showed the challenges of printing a melt-processable RTM370 imide resin powder terminated with reactive 4-phenylethynylphthalic anhydride by LS, due to its inherently low viscosity of these oligomers. This paper presented the first successful 3D printing of high temperature carbon fiber filled thermoset polyimide composites, followed by post cure cycles to promote additional crosslinking for achieving higher temperature (Tg = 370 °C) capability. The processes to build tensile specimens and a component by LS, and the characterization of RTM370 imide resin by DSC and rheology as well as evaluation of the LS printed polyimide composite specimens by SEM and mechanical tests will be discussed.

Polyimide Composites↗

Electrostrictive Graft Elastomers

An electrostrictive graft elastomer has a backbone molecule which is a non-crystallizable, flexible macromolecular chain and a grafted polymer forming polar graft moieties with backbone molecules. The polar graft moieties have been rotated by an applied electric field, e.g., into substantial polar alignment. The rotation is sustained until the electric field is removed. In another embodiment, a process for producing strain in an elastomer includes: (a) providing a graft elastomer having a backbone molecule which is a non-crystallizable, flexible macromolecular chain and a grafted polymer forming polar graft moieties with backbone molecules; and (b) applying an electric field to the graft elastomer to rotate the polar graft moieties, e.g., into substantial polar alignment.

Su, Ji↗

NMR (Nuclear Magnetic Resonance) and macromolecular migration in a melt or in concentrated solutions

The purpose of this paper is to analyze the migration process of long polymer molecules in a melt or in concentrated solutions as it may be observed from the dynamics of the transverse magnetization of nuclear spins linked to these chains. The low frequency viscoelastic relaxation of polymer systems is known to be mainly controlled by the mechanism of dissociation of topological constraints excited on chains and which are called entanglements. This mechanism exhibits a strong dependence upon the chain molecular weight. These topological constraints also govern the diffusion process of polymer chains. So, the accurate description of the diffusion motion of a chain may be a convenient way to characterize disentanglement processes necessarily involved in any model proposed to explain viscoelastic effects.

Addad, J. P. C.↗