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At least 37 records · Page 2

New polymer systems: Chain extension by dianhydrides

The results are presented for a systematic investigation on the use of anhydrides to prepare stable elastomeric materials for space use, under mild reaction conditions. The three anhydrides investigated were found to provide effective chain extension of hydroxy-terminated poly(alkylene oxides) and poly(butadienes). These were tetrahydrofuran tetracarboxylic dianhydride, pyromellitic dianhydride, and benzophenone tetracarboxylic diahydride. The most effective catalyst investigated was ferric acetylacetonate, which resulted in chain extension at 333 K (60 C). One feature of these anhydride reactants is that they are difunctional as anhydrides, but tetrafunctional if conditions are selected that lead to reaction of all carboxyl groups. Therefore, chain extension can be effected and then followed by crosslinking via the residual carboxyl groups.

Rhein, R. A.↗

New polymer systems: Chain extension by dianhydrides

Three anhydrides provide effective chain extension of hydroxy-terminated polyalkylene oxides and polybutadienes. Novel feature of these anhydride reactants is that they are difunctional as anhydrides, but they are tetrafunctional if conditions are selected that lead to total esterification or reaction of all carboxyl groups.

Rhein, R. A.↗

Graphene Oxide Reduces the Hydrolytic Degradation in Polyamide-11

Graphene oxide (GO) was incorporated into polyamide-11 (PA11) via in-situ polymerization. The GO-PA11 nano-composite had elevated resistance to hydrolytic degradation. At a loading of 1 mg/g, GO to PA11, the accelerated aging equilibrium molecular weight of GO-PA11 was higher (33 and 34 kg/mol at 100 and 120 °C, respectively) compared to neat PA11 (23 and 24 kg/mol at 100 and 120 °C, respectively). Neat PA11 had hydrolysis rate constants (kH) of 2.8 and 12 ( × 10(exp -2) day(exp -1)) when aged at 100 and 120 °C, respectively, and re-polymerization rate constants (kP) of 5.0 and 23 ( × 10(exp -5) day(exp -1)), respectively. The higher equilibrium molecular weight for GO-PA11 loaded at 1 mg/g was the result of a decreased kH, 1.8 and 4.5 ( × 10(exp -2) day(exp -1)), and an increased kP, 10 and 17 ( × 10(exp -5) day(exp -1)) compared with neat PA11 at 100 and 120 °C, respectively. The decreased rate of degradation and resulting 40% increased equilibrium molecular weight of GO-PA11 was attributed to the highly asymmetric planar GO nano-sheets that inhibited the molecular mobility of water and the polymer chain. The crystallinity of the polymer matrix was similarly affected by a reduction in chain mobility during annealing due to the GO nanoparticles' chemistry and highly asymmetric nano-planar sheet structure.

Samuel J A Hocker↗

Numerical Simulation of High Drag Reduction in a Turbulent Channel Flow with Polymer Additives

The addition of small amounts of long chain polymer molecules to wall-bounded flows can lead to dramatic drag reduction. Although this phenomenon has been known for about fifty years, the action of the polymers and its effect on turbulent structures are still unclear. Detailed experiments have characterized two distinct regimes (Warholic et al. 1999), which are referred to as low drag reduction (LDR) and high drag reduction (HDR). The first regime exhibits similar statistical trends as Newtonian flow: the log-law region of the mean velocity profile remains parallel to that of the Newtonian ow but its lower bound moves away from the wall and the upward shift of the log-region is a function of drag reduction, DR. Although streamwise fluctuations are increased and transverse ones are reduced, the shape of the rms velocity profiles is not qualitatively modified. At higher drag reductions, of the order of 40-50%, the ow enters the HDR regime for which the slope of the log-law is dramatically augmented and the Reynolds shear stress is small (Warholic et al. 1999; Ptasinski et al. 2001). The drag reduction is eventually bounded by a maximum drag reduction (MDR) (Virk & Mickley 1970) which is a function of the Reynolds number. While several experiments report mean velocity profiles very close to the empirical profile of Virk & Mickley (1970) for MDR conditions, the observations regarding the structure of turbulence can differ significantly. For instance, Warholic et al. (1999) measured a near-zero Reynolds shear stress, whereas a recent experiment (Ptasinski et al. 2001) shows evidence of non-negligible Reynolds stress in their MDR flow. To the knowledge of the authors, only the LDR regime has been documented in numerical simulations (Sureshkumar et al. 1997; Dimitropoulos et al. 1998; Min et al. 2001; Dubief & Lele 2001; Sibilla & Baron 2002). This paper discusses the simulation of polymer drag reduced channel ow at HDR using the FENE-P (Finite Elastic non-linear extensibility-Peterlin) model which was used for the first LDR simulation by Sureshkumar et al. (1997). Flow and polymer parameters are close to realistic polymer drag reducing conditions. High drag reductions are achieved by using finite differences and a robust time stepping technique. A minimal channel flow is also used as a numerical experiment to investigate the effect of the outer region turbulent structures on the overall drag at HDR. The drag reducing action of the model is finally studied through the structure of energy transfers from the polymers to the velocity components. This investigation sheds some light on the details of polymer drag reduction.

Dubief, Yves↗

New Materials for the Repair of Polyimide Electrical Wire Insulation

Two viable polyimide backbone materials have been identified that will allow the repair of polyimide electrical wire insulation found on the Space Shuttle and other aging aircraft. This identification is the outcome of ongoing efforts to assess the viability of using such polyimides and polyimide precursors (polyamic acids [PAAs]) as repair materials for aging polyimide electrical wire insulation. These repair materials were selected because they match the chemical makeup of the underlying wire insulation as closely as possible. This similarity allows for maximum compatibility, coupled with the outstanding physical properties of polyimides. The two polyimide backbone materials allow the polymer to be extremely flexible and to melt at low temperatures. A polymer chain end capping group that allows the polymer to crosslink into a nonflowable repair upon curing at around 200 C was also identified.

Source record↗

Molecules with enhanced electronic polarizabilities based on defect-like states in conjugated polymers

Highly conjugated organic polymers typically have large non-resonant electronic susceptibilities, which give the molecules unusual optical properties. To enhance these properties, defects are introduced into the polymer chain. Examples include light doping of the conjugated polymer and synthesis, conjugated polymers which incorporate either electron donating or accepting groups, and conjugated polymers which contain a photoexcitable species capable of reversibly transferring its electron to an acceptor. Such defects in the chain permit enhancement of the second hyperpolarizability by at least an order of magnitude.

Beratan, David N.↗

Thermally Stable, Piezoelectric and Pyroelectric Polymeric Substrates and Method Relating Thereto

Production of an electric voltage in response to mechanical excitation (piezoelectricity) or thermal excitation (pyroelectricity) requires a material to have a preferred dipole orientation in its structure. This preferred orientation or polarization occurs naturally in some crystals such as quartz and can be induced into some ceramic and polymeric materials by application of strong electric or mechanical fields. For some materials, a combination of mechanical and electrical orientation is necessary to completely polarize the material. The only commercially available piezoelectric polymer is poly(vinylidene fluoride) (PVF2). However, this polymer has material and process limitations which prohibit its use in numerous device applications where thermal stability is a requirement. By the present invention, thermally stable, piezoelectric and pyroelectric polymeric substrates were prepared from polymers having a softening temperature greater than 1000C. A metal electrode material is deposited onto the polymer substrate and several electrical leads are attached to it. The polymer substrate is heated in a low dielectric medium to enhance molecular mobility of the polymer chains. A voltage is then applied to the polymer substrate inducing polarization. The voltage is then maintained while the polymer substrate is cooled 'freezing in' the molecular orientation. The novelty of the invention resides in the process of preparing the piezoelectric and pyroelectric polymeric substrate. The nonobviousness of the invention is found in heating the polymeric substrate in a low dielectric medium while applying a voltage.

Simpson, Joycelyn O.↗

J-OCTA Applications to in Space Manufacturing and Nanofluidic Technologies

We consider examples of J-OCTA software application to physics-based analysis of in-space manufacturing technologies. Firstly, we consider an atomistic model of thermal welding at the polymer-polymer interface for applications to 3D manufacturing by following diffusion of polymer chains. We show that each component of the polymer blend has its own characteristic time of diffusion and that both strain–stress and shear viscosity curves agree with experimental data. Next, nonlinear shrinkage of the metal part during manufacturing by bound metal deposition under microgravity, is considered using a multi-scale physics-based approach that spans from atomistic dynamics to full-part shrinkage. At the smallest scale we use atomistic dynamics to simulated sintering of a few Ti6Al4V nanoparticles, study sintering mechanisms and estimate important parameters including grain boundary width and diffusion rates of the atoms at the surface that are used at the other scales of modelling. Finally, we analyse selective ionic conduction through an artificial nanopore in a graphene sheet motivated by applications to desalination and energy harvesting. We build distributions of the number and orientation of water molecules in the ion’s hydration shells providing novel insight into the ion-water-carbon interaction at the nanopore.

molecular dynamics↗

Theory of Transport of Long Polymer Molecules through Carbon Nanotube Channels

A theory of transport of long chain polymer molecules through carbon nanotube (CNT) channels is developed using Fokker-Planck equation and direct molecular dynamics (MD) simulations. The mean transport or translocation time tau is found to depend on the chemical potential energy, entropy and diffusion coefficient. A power law dependence tau approx. N(sup 2)is found where N is number of monomers in a molecule. For 10(exp 5)-unit long polyethylene molecules, tau is estimated to be approx. 1micro-s. The diffusion coefficient of long polymer molecules inside CNTs, like that of short ones, are found to be few orders of magnitude larger than in ordinary silicate based zeolite systems.

Wei, Chenyu↗

Protection of 2-(3-Thienyl)ethanol with 3-Thienylacetic Acid and Hard Cross- Linked Conducting Films by Electropolymerization of the Ester

The ester (compound 1) of 2-(3-thienyl)ethanol (T-etOH) with 3-thienylacetic acid was synthesized as a monomer whose two thiophene groups could be electropolymerized independently, becoming members of different polymer chains in a highly-crosslinked highly-insoluble polymer. Indeed, 1 was electropolymerized successfully alone and together with 3-methylthiophene (3MeT). Films of poly(1) are hard (3H, as opposed to less than 6B for poly(3MeT)), and the close proximity of the polymeric strands creates pi-stacking interactions. The behavior of 1 suggests that by: (a) limiting the potential used for the oxidation of monomeric esters of T-etOH at the foot of their oxidation waves (less than 1.8 V vs. Ag/AgCl); and, (b) compensating for the decrease in the electrogenerated radical concentration by increasing the monomer concentration, practically all esters of T-etOH should be electropolymerizable. This was confirmed by durable film formation from the archetypical ester of T-etOH, the 2-(3-thienyl)ethyl acetate (T-etOAc), whose homo-electropolymerization is reported for the first time.

Leventis, Nicholas↗

Optically transparent/colorless polyimides

Several series of linear aromatic polyimide films have been synthesized and characterized with the objective of obtaining maximum optical transparency. Two approaches have been used as part of this structure-property relationship study. The first approach is to vary the molecular structure so as to separate chromophoric centers and reduce electronic interactions between polymer chains to lower the intensity of color in the resulting polymer films. A second and concurrent approach is to perform polymerizations with highly purified monomers. Glass transition temperatures of thermally cured polyimide films are obtained by thermomechanical analysis and thermal decomposition temperatures are determined by thermogravimetric analysis. Transmittance UV-visible spectra of the polyimide films are compared to that of a commercial polyimide film. Fully imidized films are tested for solubility in common organic solvents. The more transparent films prepared in this study are evaluated for use on second-surface mirror thermal control coating systems. Lightly colored to colorless films are characterized by UV-visible spectroscopy before and after exposure to 300 equivalent solar hours UV irradiation and varying doses of 1 MeV electron irradiation. The effects of monomer purity, casting solvent and cure atmosphere on polyimide film transparency are also investigated.

Stclair, A. K.↗

Preparation of Proton Exchange Membranes and Lithium Batteries from Melamine-containing Ormosils

Our laboratory has recently reported a series of rodcoil polymers for lithium batteries that display dimensionally stable films with good ionic conductivity. The rod segments consist of rigid linear and branched polyimides and the coil segments are polyethylene oxides (PEO). It has been proposed that good mechanical and transport properties are due to phase separation between the rod and coil segments. It was also observed that increased branching and molecular weight lead to increased conductivity. The following study was undertaken to assess the effects of phase separation in polyalkylene oxides connected by melamine linkages. Melamine was chosen as the linking unit because it provides a branching site, cation binding sites to help ionic transport between polymer chains, and the opportunity for self assembly through hydrogen bonding. Polymers were made by the reaction of cyanuric chloride with a series of amine-terminated alkylene oxides. A linear polymer was first made, followed by reaction of the third site on cyanuric chloride with varying ratios of monofunctional Jeffamine and (3-aminopropyl)triethoxysilane. The lithium trifluoromethane sulfonamide-doped polymers are then crosslinked through a sol-gel process to form free-standing films. Initial results have shown mechanically strong films with lithium conductivities on the order of 2 x 10(exp -5) S/cm at ambient temperature. In a separate study, organically modified silanes (Ormosils) that contain sulfonic acid derivatized melamines have been incorporated into proton exchange membranes. The membranes are made by reaction of the primary amine groups of various ratios of melamine derivative and difunctional Jeffamine (MW = 2000) with the epoxide group of (3-Glycidyloxypropyl)trimethoxysilane. The films were then cross-linked through a sol-gel process. Resulting sulfuric acid doped films are strong, flexible, and have proton conductivities on the order of 2 x l0(exp -2) S/cm (120 C, 25% relative humidity). Our best results have been observed when films contain 60% PEO and 40% sulfonated melamine.

Tigelaar, Dean M.↗

Investigation of structure-property relationships in systematic series of novel polymers

Solid state transitions in polymeric materials was associated with the onset of sub-molecular motions of the polymer chains. Although these were considered to be intramolecular in general, the local environment of the polymer molecule exerts a strong influence through, for example, the effects of crystallinity, polarity and diluents. The manner of specimen preparation and previous history also affect transitions. The transitions are considered to arise when sufficient free volume is available to permit the occurrence of these side chain and backbone reorientations. The glass transition is the principal transition of amorphous polymeric materials and is associated with the onset of long range segmental motion of the polymer backbone. The various types of shorter range motion occurring below the glass transition have been catalogued.

Gillham, J. K.↗

Fundamental Studies of Low Velocity Impact Resistance of Graphite Fiber Reinforced Polymer Matrix Composites

A study was conducted to relate the impact resistance of graphite fiber reinforced composites with matrix properties through gaining an understanding of the basic mechanics involved in the deformation and fracture process, and the effect of the polymer matrix structure on these mechanisms. It was found that the resin matrix structure influences the composite impact resistance in at least two ways. The integration of flexibilizers into the polymer chain structure tends to reduce the T sub g and the mechanical properties of the polymer. The reduction in the mechanical properties of the matrix does not enhance the composite impact resistance because it allows matrix controlled failure to initiate impact damage. It was found that when the instrumented dropweight impact tester is used as a means for assessing resin toughness, the resin toughness is enhanced by the ability of the clamped specimen to deflect enough to produce sufficient membrane action to support a significant amount of the load. The results of this study indicate that crossplied composite impact resistance is very much dependent on the matrix mechanical properties.

Bowles, K. J.↗

A model for the pyrolysis of unfilled and filled polymers and comparisons with NBS smoke-density chamber data

This paper considers a model for the pyrolysis of polymers for use in mass loss and smoke density predictions in a fire situation. It is based on the fundamental postulate that the overall rate-limiting reactions are in the relatively low temperature condensed phase; the rate limiting step is the polymer degradation to a vaporizable state. The state of the polymer (chain length) at the surface is specified by the vapor pressure equilibrium criterion. For the case of polymers with inert fillers, like alumina trihydrate, the further assumption is made that the linear regression rate of the material is identical to the unfilled material's at the same surface temperature. The fraction of polymer mass loss converted to smoke is inferred from the literature. The smoke density in the NBS-smoke density chamber is predicted for a polyester and the same polyester with two different loads of alumina trihydrate filler. Diffusional effects in the smoke spreading are considered in an elementary manner. The comparisons with experimental data are encouraging. The overall fire characteristics are predicted using only the fundamental physicochemical property values of ingredients.

Kumar, R. N.↗

Polymerization Initiated at the Sidewalls of Carbon Nanotubes

A process has been developed for growing polymer chains via anionic, cationic, or radical polymerization from the side walls of functionalized carbon nanotubes, which will facilitate greater dispersion in polymer matrices, and will greatly enhance reinforcement ability in polymeric material.

Tour, James M.↗

A Model For The Burning of Teflon

Teflon has been identified as suitable material for use in oxygen-enriched atmospheres because of its low specific enthalpy of combustion that is, less than 1500 cal/gram. However, once ignited, Teflon burns in a heterogeneous reaction until total consumption or depletion of oxygen occurs. A model is developed for the burning of Teflon in pure, high-pressure oxygen, 3.4 to 68.9 MPa. The Teflon polymer chain dissociates via monomer units due to pyrolysis. These monomer units diffuse to the surface due to free convection. The model consists of coupled mass and energy balances for the polymer and an energy balance for the free convection of product gases. The model is used to obtain appropriate kinetic parameters for the dissociation and surface reactions. The model is validated against experimental measurements of Teflon discs supported on aluminum rods (2216) at oxygen pressures of 3.4, 6.8, 34.4, and 68.9 MPa. The model simulates the temperature distribution in the product gases above burning Teflon.

Waller, Jess M.↗