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Sample records for polymer network membrane

  1. Membrane consisting of polyquaternary amine ion exchange polymer network interpenetrating the chains of thermoplastic matrix polymer

    NASA Technical Reports Server (NTRS)

    Rembaum, A.; Wallace, C. J. (Inventor)

    1978-01-01

    An ion exchange membrane was formed from a solution containing dissolved matrix polymer and a set of monomers which are capable of reacting to form a polyquaternary ion exchange material; for example vinyl pyride and a dihalo hydrocarbon. After casting solution and evaporation of the volatile component's, a relatively strong ion exchange membrane was obtained which is capable of removing anions, such as nitrate or chromate from water. The ion exchange polymer forms an interpenetrating network with the chains of the matrix polymer.

  2. Interpenetrating polymer network ion exchange membranes and method for preparing same

    DOEpatents

    Alexandratos, Spiro D.; Danesi, Pier R.; Horwitz, E. Philip

    1989-01-01

    Interpenetrating polymer network ion exchange membranes include a microporous polymeric support film interpenetrated by an ion exchange polymer and are produced by absorbing and polymerizing monomers within the support film. The ion exchange polymer provides ion exchange ligands at the surface of and throughout the support film which have sufficient ligand mobility to extract and transport ions across the membrane.

  3. Multifunctional membranes for solvent resistant nanofiltration and pervaporation applications based on segmented polymer networks.

    PubMed

    Li, Xianfeng; Basko, Malgorzata; Du Prez, S Filip; Vankelecom, Ivo F J

    2008-12-25

    Hydrophilic bis(acrylate)-terminated poly(ethylene oxide) was used as macromolecular cross-linker of different hydrophobic polyacrylates for the synthesis of amphiphilic segmented polymer networks (SPNs). Multifunctional composite membranes with thin SPN toplayers were prepared by in situ polymerization. As the support consisted of hydrolyzed polyacrylonitrile, the high chemical resistance of the composite membrane allowed applications of the SPN-based membranes in solvent-resistant nanofiltration (SRNF) and pervaporation (PV). The membranes show very high retention on Rose Bengal (RB) in different solvents, especially in strong swelling solvents such as tetrahydrofuran (THF) and dimethylformamide (DMF). The membranes were also tested in pervaporation for dehydration of ethanol and isopropanol (IPA). The selectivity of the membranes greatly depends on the composition or the ratio of the hydrophilic and hydrophobic phases of the SPN. PMID:19055387

  4. Stability in alkaline aqueous electrolyte of air electrode protected with fluorinated interpenetrating polymer network membrane

    NASA Astrophysics Data System (ADS)

    Bertolotti, Bruno; Messaoudi, Houssam; Chikh, Linda; Vancaeyzeele, Cédric; Alfonsi, Séverine; Fichet, Odile

    2015-01-01

    We developed original anion exchange membranes to protect air electrodes operating in aqueous lithium-air battery configuration, i.e. supplied with atmospheric air and in concentrated aqueous lithium hydroxide. These protective membranes have an interpenetrating polymer network (IPN) architecture combining a hydrogenated cationic polyelectrolyte network based on poly(epichlorohydrin) (PECH) and a fluorinated neutral network based on perfluoropolyether (Fluorolink® MD700). Two phases, each one rich in one of the polymer, are co-continuous in the materials. This morphology allows combining their properties according to the weight proportions of each polymer. Thus, PECH/Fluorolink IPNs show ionic conductivity varying from 1 to 2 mS cm-1, water uptake from 30 to 90 wt.% and anionic transport number from 0.65 to 0.80 when the PECH proportion varies from 40 to 90 wt.%. These membranes have been systematically assembled on air electrodes. Air electrode protected with PECH/Fluorolink 70/30 IPN shows outstanding stability higher than 1000 h, i.e. a 20-fold increase in the lifetime of the non-modified electrode. This efficient membrane/air electrode assembly is promising for development of alkaline electrolyte based storage or production energy systems, such as metal air batteries or alkaline fuel cells.

  5. Chemical compatibility of PU/PAN interpenetrating polymer network membrane with substituted aromatic solvents.

    PubMed

    Kumar, H; Siddaramaiah

    2007-09-01

    Polyethylene glycol (PEG)-based polyurethane/polyacrylonitrile (PU/PAN, 50/50) semi-interpenetrating polymer network (SIPN) membrane has been studied from sorption/desorption cycles and diffusion behaviour with substituted aromatic probe molecules at 20, 40 and 60 degrees C. Sorption/desorption cycles have been repeated to evaluate polymer-solvent interaction. Organic solvents taken up or given out by IPN are measured periodically till equilibrium. Using these data, sorption (S), diffusion (D) and permeation (P) coefficients have been calculated from Fick's equation. Sorption data is correlated with solubility parameter of solvents and polymer. It was found that solvents of comparable solubility parameter with IPN interact more and thus there is an increase in sorption. Molecular mass between cross-link has been calculated using Flory Rehner equation. The cross-link density and degree of cross-linking of the membrane is calculated. From the temperature dependence of sorption and diffusion coefficients, the Arrhenius activation parameters like activation energy for diffusion (E(D)) and permeation (E(P)) processes have been calculated. Furthermore, the sorption results have been interpreted in terms of thermodynamic parameters such as change in enthalpy (DeltaH) and entropy (DeltaS). Concentration profiles of penetrants at different penetration depths in the polymer sample at different time intervals have also been calculated theoretically from a solution of Fick's equation under appropriate initial boundary conditions. PMID:17418943

  6. Polymers at membranes

    NASA Astrophysics Data System (ADS)

    Breidenich, Markus

    2000-11-01

    The surface of biological cells consists of a lipid membrane and a large amount of various proteins and polymers, which are embedded in the membrane or attached to it. We investigate how membranes are influenced by polymers, which are anchored to the membrane by one end. The entropic pressure exerted by the polymer induces a curvature, which bends the membrane away from the polymer. The resulting membrane shape profile is a cone in the vicinity of the anchor segment and a catenoid far away from it. The perturbative calculations are confirmed by Monte-Carlo simulations. An additional attractive interaction between polymer and membrane reduces the entropically induced curvature. In the limit of strong adsorption, the polymer is localized directly on the membrane surface and does not induce any pressure, i.e. the membrane curvature vanishes. If the polymer is not anchored directly on the membrane surface, but in a non-vanishing anchoring distance, the membrane bends towards the polymer for strong adsorption. In the last part of the thesis, we study membranes under the influence of non-anchored polymers in solution. In the limit of pure steric interactions between the membrane and free polymers, the membrane curves towards the polymers (in contrast to the case of anchored polymers). In the limit of strong adsorption the membrane bends away from the polymers. Die Oberfläche biologischer Zellen besteht aus einer Lipidmembran und einer Vielzahl von Proteinen und Polymeren, die in die Membran eingebaut sind. Die Beeinflussung der Membran durch Polymere, die mit einem Ende an der Membran verankert sind, wird im Rahmen dieser Arbeit anhand eines vereinfachten biomimetischen Systems studiert. Der entropische Druck, den das Polymer durch Stöße auf die Membran ausübt, führt dazu, dass sich die Membran vom Polymer weg krümmt. Die resultierende Membranform ist ein Kegel in der Nähe des Ankers und ein Katenoid in grossem Abstand vom Ankerpunkt. Monte Carlo-Simulationen best

  7. High-Performance of PEI/Nafion/ox-MWCNT Composite Membranes Based on Semi-Interpenetrating Polymer Networks for PEMFCs.

    PubMed

    Kim, Hee Jin; Talukdar, Krishan; Kim, Young Ho; Lee, Ho-Chang; Choi, Sang-June

    2015-11-01

    Polymer electrolyte membrane fuel cells (PEMFCs) are an up-and-coming technology for green and efficient power generation and offer a clean alternative to current technologies that use hydrocarbon fuel sources. In this paper, a reinforcing membrane was fabricated by Polyethylenimine polymer. Oxidized multiwalled carbon nanotube was dispersed into the PEI/Nafion membranes to achieve additional strength. The membranes were acidified via absorption of phosphoric acid from aqueous solution to make semi-interpenetrating polymer network (s-IPNs) which increases the proton conductivity by producing proton channel in the membrane. The PEI/Nafion/ox-MWCNT composite membranes show excellent phosphoric acid retention and high humidity, which impart a high ion exchange capacity (IEC) as well as improved proton conductivity. The surface morphologies and cross-sections of the resulting H3PO4 treated PEI/Nafion/ox-MWCNT composite membranes were observed using optical microscopy and scanning electron microscopy (SEM). The improvements in the thermal properties of the prepared PEI/Nafion/ox-MWCNT composite membranes were determined using thermogravimetric analysis (TGA). These performance results combined with the low inexpensive synthetic approach substantiate the potential for the new membrane to be used in PEMFCs. PMID:26726601

  8. Long lifetime in concentrated LiOH aqueous solution of air electrode protected with interpenetrating polymer network membrane

    NASA Astrophysics Data System (ADS)

    Ghamouss, Fouad; Mallouki, Mohamed; Bertolotti, Bruno; Chikh, Linda; Vancaeyzeele, Cédric; Alfonsi, Séverine; Fichet, Odile

    2012-01-01

    Solid anion-exchange membranes that display interpenetrating polymer network (IPN) architecture were developed to be assembled on air electrode surface to improve its electrochemical stability in alkaline environment. The IPN membranes associate an anionic conducting polyepichlorohydrin network entangled within a cross-linked poly(2-hydroxyethyl methacrylate) in different mass proportions. The membranes possess suitable mechanical and thermal properties, an ionic conductivity of about 1 × 10-3 S cm-1 and suitable cation selectivity. The electrochemical behaviour of the air electrode/IPN membrane assemblies (AEMA) were then evaluated in LiOH 5 M. The polarization curves indicate that a good electrochemical interface was established between the electrode and the IPN membranes. Moreover, the AEMA exhibits a discharge stability in LiOH 5 M ten times higher compared to a bare electrode under the same conditions.

  9. Proton-conducting electrolyte membranes based on organosiloxane network/sulfonated poly(ether ether ketone) interpenetrating polymer networks embedding sulfonated mesoporous benzene-silica

    NASA Astrophysics Data System (ADS)

    Han, Sung Yeon; Park, Junghwa; Kim, Dukjoon

    2013-12-01

    Composite membranes based on organosiloxane network (OSPN)/sulfonated poly(ether ether ketone) (SPEEK) interpenetrating polymer network (IPN) structures with sulfonated mesoporous benzene-silica (SMBS) proton conductors embedded are fabricated. The flexibility and toughness properties of OSPN are expected to compensate for the brittleness of the sPEEK membranes. The 2D-hexagonal cylindrical mesopore structures of SMBS maintain the water content at a high level to enhance the conductivity, even at low relative humidity. Compared to the pristine sPEEK membranes, the ternary composite membranes can endure about 10 times more elongation before breaking. Both OSPN and SMBS components enhance the proton conductivity of sPEEK membranes in a hydrated state, while maintaining the water uptake at below 55% even at temperatures as high as 100 °C. The SAXS patterns of the composite membranes explain the water-related membrane properties of composite membranes. The maximum power densities of Nafion membrane-based MEAs are 178.4 mA cm-2, 132.2 mA cm-2, and 90.9 mA cm-2, but those of composite membrane-based ones are 159.1 mA cm-2, 134.2 mA cm-2, and 110.8 mA cm-2 at 95%, 70%, and 45% relative humidity, respectively.

  10. Covalent organic/inorganic hybrid proton-conductive membrane with semi-interpenetrating polymer network: Preparation and characterizations

    NASA Astrophysics Data System (ADS)

    Fu, Rong-Qiang; Woo, Jung-Je; Seo, Seok-Jun; Lee, Jae-Suk; Moon, Seung-Hyeon

    2008-05-01

    A series of new covalent organic/inorganic hybrid proton-conductive membranes, each with a semi-interpenetrating polymer network (semi-IPN), for direct methanol fuel cell (DMFC) applications is prepared through the following sequence: (i) copolymerization of impregnated styrene (St), p-vinylbenzyl chloride (VBC) and divinylbenzene (DVB) within a supporting polyvinyl chloride (PVC) film; (ii) reaction of the chloromethyl group with 3-(methylamine)propyl-trimethoxysilane (MAPTMS); (ii) a sol-gel process under acidic conditions; (iv) a sulfonation reaction. The developed membranes are characterized in terms of Fourier transform infrared/attenuated total reflectance (FTIR/ATR), scanning electron microscopy/energy-dispersive X-ray analysis (SEM/EDXA), elemental analysis (EA) and thermogravimetric analysis (TGA), which confirm the formation of the target membranes. The developed copolymer chains are interpenetrating with the PVC matrix to form the semi-IPN structure, and the inorganic silica is covalently bound to the copolymers. These features provide the membranes with high mechanical strength. The effect of silica content is investigated. As the silica content increases, proton conductivity and water content decrease, whereas oxidative stability is improved. In particular, methanol permeability and methanol uptake are reduced largely by the silica. The ratio of proton conductivity to methanol permeability for the hybrid membranes is higher than that of Nafion 117. All these properties make the hybrid membranes a potential candidate for DMFC applications.

  11. Composite solid polymer electrolyte membranes

    SciTech Connect

    Formato, Richard M.; Kovar, Robert F.; Osenar, Paul; Landrau, Nelson; Rubin, Leslie S.

    2006-05-30

    The present invention relates to composite solid polymer electrolyte membranes (SPEMs) which include a porous polymer substrate interpenetrated with an ion-conducting material. SPEMs of the present invention are useful in electrochemical applications, including fuel cells and electrodialysis.

  12. Composite solid polymer electrolyte membranes

    DOEpatents

    Formato, Richard M.; Kovar, Robert F.; Osenar, Paul; Landrau, Nelson; Rubin, Leslie S.

    2001-06-19

    The present invention relates to composite solid polymer electrolyte membranes (SPEMs) which include a porous polymer substrate interpenetrated with an ion-conducting material. SPEMs of the present invention are useful in electrochemical applications, including fuel cells and electrodialysis.

  13. Layered plasma polymer composite membranes

    DOEpatents

    Babcock, W.C.

    1994-10-11

    Layered plasma polymer composite fluid separation membranes are disclosed, which comprise alternating selective and permeable layers for a total of at least 2n layers, where n is [>=]2 and is the number of selective layers. 2 figs.

  14. Pore Network Modeling and Synchrotron Imaging of Liquid Water in the Gas Diffusion Layer of Polymer Electrolyte Membrane Fuel Cells

    NASA Astrophysics Data System (ADS)

    Hinebaugh, James Thomas

    Polymer electrolyte membrane (PEM) fuel cells operate at levels of high humidity, leading to condensation throughout the cell components. The porous gas diffusion layer (GDL) must not become over-saturated with liquid water, due to its responsibility in providing diffusion pathways to and from the embedded catalyst sites. Due to the opaque and microscale nature of the GDL, a current challenge of the fuel cell industry is to identify the characteristics that make the GDL more or less robust against flooding. Modeling the system as a pore network is an attractive investigative strategy; however, for flooding simulations to provide meaningful material comparisons, accurate GDL topology and condensation distributions must be provided. The focus of this research is to provide the foundational tools with which to capture both of these requirements. The method of pore network modeling on topologically representative pore networks is demonstrated to describe flooding phenomena within GDL materials. A stochastic modeling algorithm is then developed to create pore spaces with the relevant features of GDL materials. Then, synchrotron based X-ray visualization experiments are developed and conducted to provide insight into condensation conditions. It was found that through-plane porosity distributions have significant effects on the GDL saturation levels. Some GDL manufacturing processes result in high porosity regions which are predicted to become heavily saturated with water if they are positioned between the condensation sites and the exhaust channels. Additionally, it was found that fiber diameter and the volume fraction of binding material applied to the GDL have significant impacts on the GDL heterogeneity and pore size distribution. Representative stochastic models must accurately describe these three material characteristics. In situ, dynamic liquid water behavior was visualized at the Canadian Light source, Inc. synchrotron using imaging and image processing

  15. Solid polymer membrane program

    NASA Technical Reports Server (NTRS)

    1971-01-01

    The results are presented for a solid polymer electrolyte fuel cell development program. Failure mechanism was identified and resolution of the mechanism experienced in small stack testing was demonstrated. The effect included laboratory analysis and evaluation of a matrix of configurations and operational variables for effects on the degree of hydrogen fluoride released from the cell and on the degree of blistering/delamination occurring in the reactant inlet areas of the cell and to correlate these conditions with cell life capabilities. The laboratory evaluation tests were run at conditions intended to accelerate the degradation of the solid polymer electrolyte in order to obtain relative evaluations as quick as possible. Evaluation of the resolutions for the identified failure mechanism in space shuttle configuration cell assemblies was achieved with the fabrication and life testing of two small stack buildups of four cell assemblies and eight cells each.

  16. Influence of membrane structure on the operating current densities of non-aqueous redox flow batteries: Organic-inorganic composite membranes based on a semi-interpenetrating polymer network

    NASA Astrophysics Data System (ADS)

    Shin, Sung-Hee; Kim, Yekyung; Yun, Sung-Hyun; Maurya, Sandip; Moon, Seung-Hyeon

    2015-11-01

    We develop three types of organic-inorganic composite membranes based on a semi-interpenetrating polymer network (SIPN) to explore the effects of membrane structure on the possible operating current densities of a non-aqueous redox flow battery (RFB) system. Poly(vinylidene fluoride) (PVdF) is selected as a supporting polymer matrix for improving the chemical and thermal stability of the organic-inorganic composite membranes. We also introduce silica nanoparticles (5 wt% of PVdF) into the membranes to ensure the low crossover of active species. The fabrication of SIPN through the addition of glycidyl methacrylate, 4-vinylpyridine, or N-vinylcarbazole enables control of the membrane structure. Depending on monomer type, the membrane structure is determined to be either aliphatic or aromatic in terms of chemical properties and either dense or porous in terms of physical properties. These chemical and physical structures affect the electrochemical properties that correspond to charge/discharge performance and to the range of possible operating current densities. An important requirement is to examine charge/discharge performance at the possible range of operating current densities by using various membrane structures. This requirement is discussed in relation to a proposed design strategy for non-aqueous RFB membranes.

  17. Electronic polymers in lipid membranes

    PubMed Central

    Johansson, Patrik K.; Jullesson, David; Elfwing, Anders; Liin, Sara I.; Musumeci, Chiara; Zeglio, Erica; Elinder, Fredrik; Solin, Niclas; Inganäs, Olle

    2015-01-01

    Electrical interfaces between biological cells and man-made electrical devices exist in many forms, but it remains a challenge to bridge the different mechanical and chemical environments of electronic conductors (metals, semiconductors) and biosystems. Here we demonstrate soft electrical interfaces, by integrating the metallic polymer PEDOT-S into lipid membranes. By preparing complexes between alkyl-ammonium salts and PEDOT-S we were able to integrate PEDOT-S into both liposomes and in lipid bilayers on solid surfaces. This is a step towards efficient electronic conduction within lipid membranes. We also demonstrate that the PEDOT-S@alkyl-ammonium:lipid hybrid structures created in this work affect ion channels in the membrane of Xenopus oocytes, which shows the possibility to access and control cell membrane structures with conductive polyelectrolytes. PMID:26059023

  18. Low Crossover Polymer Electrolyte Membranes for Direct Methanol Fuel Cells

    NASA Technical Reports Server (NTRS)

    Prakash, G. K. Surya; Smart, Marshall; Atti, Anthony R.; Olah, George A.; Narayanan, S. R.; Valdez, T.; Surampudi, S.

    1996-01-01

    Direct Methanol Fuel Cells (DMFC's) using polymer electrolyte membranes are promising power sources for portable and vehicular applications. State of the art technology using Nafion(R) 117 membranes (Dupont) are limited by high methanol permeability and cost, resulting in reduced fuel cell efficiencies and impractical commercialization. Therefore, much research in the fuel cell field is focused on the preparation and testing of low crossover and cost efficient polymer electrolyte membranes. The University of Southern California in cooperation with the Jet Propulsion Laboratory is focused on development of such materials. Interpenetrating polymer networks are an effective method used to blend polymer systems without forming chemical links. They provide the ability to modify physical and chemical properties of polymers by optimizing blend compositions. We have developed a novel interpenetrating polymer network based on poly (vinyl - difluoride)/cross-linked polystyrenesulfonic acid polymer composites (PVDF PSSA). Sulfonation of polystyrene accounts for protonic conductivity while the non-polar, PVDF backbone provides structural integrity in addition to methanol rejection. Precursor materials were prepared and analyzed to characterize membrane crystallinity, stability and degree of interpenetration. USC JPL PVDF-PSSA membranes were also characterized to determine methanol permeability, protonic conductivity and sulfur distribution. Membranes were fabricated into membrane electrode assemblies (MEA) and tested for single cell performance. Tests include cell performance over a wide range of temperatures (20 C - 90 C) and cathode conditions (ambient Air/O2). Methanol crossover values are measured in situ using an in-line CO2 analyzer.

  19. Mechanisms of gas permeation through polymer membranes

    SciTech Connect

    Stern, S.A.

    1991-01-01

    The objective of the present study is to investigate the mechanisms of gas transport in and through polymer membranes and the dependence of these mechanisms on pressure and temperature. This information is required for the development of new, energy-efficient membrane processes for the separation of industrial gas mixtures. Such processes are based on the selective permeation of the components of gas mixtures through nonporous polymer membranes. Recent work has been focused on the permeation of gases through membranes made from glassy polymers, i.e., at temperatures below the glass transition of the polymers (Tg). Glassy polymers are very useful membrane materials for gas separations because of their high selectivity toward different gases. Gases permeate through nonporous polymer membranes by a solution-diffusion'' process. Consequently, in order to understand the characteristics of this process it is necessary to investigate also the mechanisms of gas solution and diffusion in glassy polymers. 23 refs., 10 figs., 4 tabs.

  20. Semi-Interpenetrating Polymer Networks

    NASA Technical Reports Server (NTRS)

    St. Clair, T. L.; Egli, A. O.

    1987-01-01

    Desirable qualities achieved by "networking" aromatic and addition polyimides. Novel semi-interpenetrating network (semi-ipn) prepared from two types of polyimides. Semi-ipn results when linear polymer synthesized in presence of cross-linked polymer or vice-versa. Semi-ipn attains certain properties better than those of either polymer alone.

  1. Stretchable and strong cellulose nanopaper structures based on polymer-coated nanofiber networks: an alternative to nonwoven porous membranes from electrospinning.

    PubMed

    Sehaqui, Houssine; Morimune, Seira; Nishino, Takashi; Berglund, Lars A

    2012-11-12

    Nonwoven membranes based on electrospun fibers are of great interest in applications such as biomedical, filtering, and protective clothing. The poor mechanical performance is a limitation, as is some of the electrospinning solvents. To address these problems, porous nonwoven membranes based on nanofibrillated cellulose (NFC) modified by a hydroxyethyl cellulose (HEC) polymer coating are prepared. NFC/HEC aqueous suspensions are subjected to simple vacuum filtration in a paper-making fashion, followed by supercritical CO(2) drying. These nonwoven nanocomposite membranes are truly nanostructured and exhibit a nanoporous network structure with high specific surface area, as analyzed by nitrogen adsorption and FE-SEM. Mechanical properties evaluated by tensile tests show high strength combined with remarkably high strain to failure of up to 55%. XRD analysis revealed significant fibril realignment during tensile stretching. After postdrawing of the random mats, the modulus and strength are strongly increased. The present preparation route uses components from renewable resources, is environmentally friendly, and results in permeable membranes of exceptional mechanical performance. PMID:23046114

  2. Flows in Polymer Networks

    NASA Astrophysics Data System (ADS)

    Tanaka, Fumihiko

    A simple transient network model is introduced to describe creation and annihilation of junctions in the networks of associating polymers. Stationary non-linear viscosity is calculated by the theory and by Monte Carlo simulation to study shear thickening. The dynamic mechanical moduli are calculated as functions of the frequency and the chain disengagement rate. From the peak of the loss modulus, the lifetime τx of the junction is estimated, and from the high frequency plateau of the storage modulus, the number of elastically effective chains in the network is found. Transient phenomena such as stress relaxation and stress overshoot are also theoretically studied. Results are compared with the recent experimental reports on the rheological study of hydrophobically modified water-soluble polymeters.

  3. Electroelasticity of polymer networks

    NASA Astrophysics Data System (ADS)

    Cohen, Noy; Dayal, Kaushik; deBotton, Gal

    2016-07-01

    A multiscale analysis of the electromechanical coupling in elastic dielectrics is conducted, starting from the discrete monomer level through the polymer chain and up to the macroscopic level. Three models for the local relations between the molecular dipoles and the electric field that can fit a variety of dipolar monomers are considered. The entropy of the network is accounted for within the framework of statistical mechanics with appropriate kinematic and energetic constraints. At the macroscopic level closed-form explicit expressions for the behaviors of amorphous dielectrics and isotropic polymer networks are determined, none of which admits the commonly assumed linear relation between the polarization and the electric field. The analysis reveals the dependence of the macroscopic coupled behavior on three primary microscopic parameters: the model assumed for the local behavior, the intensity of the local dipole, and the length of the chain. We show how these parameters influence the directional distributions of the monomers and the hence the resulting overall response of the network. In particular, the dependences of the polarization and the polarization induced stress on the deformation of the dielectric are illustrated. More surprisingly, we also reveal a dependence of the stress on the electric field which stems from the kinematic constraint imposed on the chains.

  4. Nanostructured polymer membranes for proton conduction

    DOEpatents

    Balsara, Nitash Pervez; Park, Moon Jeong

    2013-06-18

    Polymers having an improved ability to entrain water are characterized, in some embodiments, by unusual humidity-induced phase transitions. The described polymers (e.g., hydrophilically functionalized block copolymers) have a disordered state and one or more ordered states (e.g., a lamellar state, a gyroid state, etc.). In one aspect, the polymers are capable of undergoing a disorder-to-order transition while the polymer is exposed to an increasing temperature at a constant relative humidity. In some aspects the polymer includes a plurality of portions, wherein a first portion forms proton-conductive channels within the membrane and wherein the channels have a width of less than about 6 nm. The described polymers are capable of entraining and preserving water at high temperature and low humidity. Surprisingly, in some embodiments, the polymers are capable of entraining greater amounts of water with the increase of temperature. The polymers can be used in Polymer Electrolyte Membranes in fuel cells.

  5. Optical-Quality Thin Polymer Membranes

    NASA Technical Reports Server (NTRS)

    Moore, James; Patrick, Brian

    2003-01-01

    A method of fabricating both curved and flat thin polymer membranes of optical quality has been developed. The method was originally intended to enable the fabrication of lightweight membrane imaging and interferometric optics, possibly with apertures multiple meters wide, for use in scientific instruments that would operate in outer space. The method may also be applicable to the fabrication of lightweight membrane optics for terrestrial use. The method involves flow-casting of a soluble polymer with mechanical and environmental controls that provide nearly ideal conditions for the formation of a membrane. The preferred environmental conditions and other details of the process depend on the choice of polymer and substrate material and on the shape and size of the membrane to be cast. Once the polymer has dried to a membrane, it is cured with convective heating, then released. Membranes with root-mean-square surface roughnesses of less than 10.5 can be produced routinely by this method. Variations in the thicknesses of the membranes have ranged from 1/3 wavelength down to as little as 1/20 wavelength (at a wavelength of 633 nm). Membranes fabricated thus far have had diameters up to 0.5 m, and there appears to be no major obstacle to scaling up to multiple-meter diameters.

  6. Anion-conducting polymer, composition, and membrane

    DOEpatents

    Pivovar, Bryan S.; Thorn, David L.

    2011-11-22

    Anion-conducing polymers and membranes with enhanced stability to aqueous alkali include a polymer backbone with attached sulfonium, phosphazenium, phosphazene, and guanidinium residues. Compositions also with enhanced stability to aqueous alkali include a support embedded with sulfonium, phosphazenium, and guanidinium salts.

  7. Fuel cell electrolyte membrane with basic polymer

    DOEpatents

    Larson, James M.; Pham, Phat T.; Frey, Matthew H.; Hamrock, Steven J.; Haugen, Gregory M.; Lamanna, William M.

    2010-11-23

    The present invention is an electrolyte membrane comprising an acid and a basic polymer, where the acid is a low-volatile acid that is fluorinated and is either oligomeric or non-polymeric, and where the basic polymer is protonated by the acid and is stable to hydrolysis.

  8. Fuel cell electrolyte membrane with basic polymer

    DOEpatents

    Larson, James M.; Pham, Phat T.; Frey, Matthew H.; Hamrock, Steven J.; Haugen, Gregory M.; Lamanna, William M.

    2012-12-04

    The present invention is an electrolyte membrane comprising an acid and a basic polymer, where the acid is a low-volatile acid that is fluorinated and is either oligomeric or non-polymeric, and where the basic polymer is protonated by the acid and is stable to hydrolysis.

  9. Anion-Conducting Polymer, Composition, and Membrane

    SciTech Connect

    Pivovar, Bryan S.; Thorn, David L.

    2008-10-21

    Anion-conducing polymers and membranes with enhanced stability to aqueous alkali include a polymer backbone with attached sulfonium, phosphazenium, phosphazene, and guanidinium residues. Compositions also with enhanced stability to aqueous alkali include a support embedded with sulfonium, phosphazenium, and guanidinium salts.

  10. Anion-conducting polymer, composition, and membrane

    DOEpatents

    Pivovar, Bryan S.; Thorn, David L.

    2010-12-07

    Anion-conducing polymers and membranes with enhanced stability to aqueous alkali include a polymer backbone with attached sulfonium, phosphazenium, phosphazene, and guanidinium residues. Compositions also with enhanced stability to aqueous alkali include a support embedded with sulfonium, phosphazenium, and guanidinium salts.

  11. Anion-conducting polymer, composition, and membrane

    DOEpatents

    Pivovar, Bryan S.; Thorn, David L.

    2009-09-01

    Anion-conducing polymers and membranes with enhanced stability to aqueous alkali include a polymer backbone with attached sulfonium, phosphazenium, phosphazene, and guanidinium residues. Compositions also with enhanced stability to aqueous alkali include a support embedded with sulfonium, phosphazenium, and guanidinium salts.

  12. Macroscopic Modeling of Polymer-Electrolyte Membranes

    SciTech Connect

    Weber, A.Z.; Newman, J.

    2007-04-01

    In this chapter, the various approaches for the macroscopic modeling of transport phenomena in polymer-electrolyte membranes are discussed. This includes general background and modeling methodologies, as well as exploration of the governing equations and some membrane-related topic of interest.

  13. Ending Aging in Super Glassy Polymer Membranes

    SciTech Connect

    Lau, CH; Nguyen, PT; Hill, MR; Thornton, AW; Konstas, K; Doherty, CM; Mulder, RJ; Bourgeois, L; Liu, ACY; Sprouster, DJ; Sullivan, JP; Bastow, TJ; Hill, AJ; Gin, DL; Noble, RD

    2014-04-16

    Aging in super glassy polymers such as poly(trimethylsilylpropyne) (PTMSP), poly(4-methyl-2-pentyne) (PMP), and polymers with intrinsic microporosity (PIM-1) reduces gas permeabilities and limits their application as gas-separation membranes. While super glassy polymers are initially very porous, and ultra-permeable, they quickly pack into a denser phase becoming less porous and permeable. This age-old problem has been solved by adding an ultraporous additive that maintains the low density, porous, initial stage of super glassy polymers through absorbing a portion of the polymer chains within its pores thereby holding the chains in their open position. This result is the first time that aging in super glassy polymers is inhibited whilst maintaining enhanced CO2 permeability for one year and improving CO2/N-2 selectivity. This approach could allow super glassy polymers to be revisited for commercial application in gas separations.

  14. Spray forming polymer membranes, coatings and films

    DOEpatents

    McHugh, K.M.; Watson, L.D.; McAtee, R.E.; Ploger, S.A.

    1993-10-12

    A method is described for forming a polymer film having controlled physical and chemical characteristics, wherein a plume of nebulized droplets of a polymer or polymer precursor is directed toward a substrate from a converging/diverging nozzle having a throat at which the polymer or a precursor thereof is introduced and an exit from which the nebulized droplets of the polymer or precursor thereof leave entrained in a carrier gas. Relative movement between the nozzle and the substrate is provided to form a polymer film. Physical and chemical characteristics can be controlled by varying the deposition parameters and the gas and liquid chemistries. Semipermeable membranes of polyphosphazene films are disclosed, as are a variety of other polymer systems, both porous and non-porous. 4 figures.

  15. Spray forming polymer membranes, coatings and films

    DOEpatents

    McHugh, Kevin M.; Watson, Lloyd D.; McAtee, Richard E.; Ploger, Scott A.

    1993-01-01

    A method of forming a polymer film having controlled physical and chemical characteristics, wherein a plume of nebulized droplets of a polymer or polymer precursor is directed toward a substrate from a converging/diverging nozzle having a throat at which the polymer or a precursor thereof is introduced and an exit from which the nebulized droplets of the polymer or precursor thereof leave entrained in a carrier gas. Relative movement between the nozzle and the substrate is provided to form a polymer film. Physical and chemical characteristics can be controlled by varying the deposition parameters and the gas and liquid chemistries. Semipermeable membranes of polyphosphazene films are disclosed, as are a variety of other polymer systems, both porous and non-porous.

  16. Advanced composite polymer electrolyte fuel cell membranes

    SciTech Connect

    Wilson, M.S.; Zawodzinski, T.A.; Gottesfeld, S.; Kolde, J.A.; Bahar, B.

    1995-09-01

    A new type of reinforced composite perfluorinated polymer electrolyte membrane, GORE-SELECT{trademark} (W.L. Gore & Assoc.), is characterized and tested for fuel cell applications. Very thin membranes (5-20 {mu}m thick) are available. The combination of reinforcement and thinness provides high membrane, conductances (80 S/cm{sup 2} for a 12 {mu}m thick membrane at 25{degrees}C) and improved water distribution in the operating fuel cell without sacrificing longevity or durability. In contrast to nonreinforced perfluorinated membranes, the x-y dimensions of the GORE-SELECT membranes are relatively unaffected by the hydration state. This feature may be important from the viewpoints of membrane/electrode interface stability and fuel cell manufacturability.

  17. Light Responsive Polymer Membranes: A Review

    PubMed Central

    Nicoletta, Fiore Pasquale; Cupelli, Daniela; Formoso, Patrizia; De Filpo, Giovanni; Colella, Valentina; Gugliuzza, Annarosa

    2012-01-01

    In recent years, stimuli responsive materials have gained significant attention in membrane separation processes due to their ability to change specific properties in response to small external stimuli, such as light, pH, temperature, ionic strength, pressure, magnetic field, antigen, chemical composition, and so on. In this review, we briefly report recent progresses in light-driven materials and membranes. Photo-switching mechanisms, valved-membrane fabrication and light-driven properties are examined. Advances and perspectives of light responsive polymer membranes in biotechnology, chemistry and biology areas are discussed. PMID:24957966

  18. Conducting polymer membranes as intelligent separation systems

    SciTech Connect

    Price, W.E.; Wallace, G.G.

    1994-12-31

    Conducting electroactive polymers such as polypyrroles, are emerging as excellent materials in which to base a generic technology for the development of intelligent material systems. They are easy to make and many different chemistries may be built in during synthesis by varying the polymer(s) used and the counterions incorporated. However, the unique feature about them is that they have dynamic chemical and physical properties which may be manipulated via changing the redox states after synthesis. This paper illustrates their potential using recent work on developing a new electro-membrane separation technology using free-standing polypyrrole films. These systems are shown to be capable of a high degree of permselectivity and controllable transport that may be turned on and off by application of potential to the conducting polymer membrane.

  19. Membranes and Films from Polymers.

    ERIC Educational Resources Information Center

    Blumberg, Avrom A.

    1986-01-01

    Provides background information on polymeric films and membranes including production methods, special industrial and medical applications, laboratory preparation, and an experimental investigation of a porous cellulose acetate membrane. Presents a demonstration to distinguish between high- and low-density polyethylene. (JM)

  20. Polymer synthesis toward fuel cell membrane materials

    NASA Astrophysics Data System (ADS)

    Rebeck, Nathaniel T.

    Fuel cells are a promising technology that will be part of the future energy landscape. New membranes for alkaline and proton exchange membrane fuel cells are needed to improve the performance, simplify the system, and reduce cost. Polymer chemistry can be applied to develop new polymers and to assemble polymers into improved membranes that need less water, have increased performance and are less expensive, thereby removing the deficiencies of current membranes. Nucleophilic aromatic substitution polymerization typically produces thermally stable engineering polymers that can be easily functionalized. New functional monomers were developed to explore new routes to novel functional polymers. Sulfonamides were discovered as new activating groups for polymerization of high molecular weight thermooxidatively stable materials with sulfonic acid latent functionality. While the sulfonamide functional polymers could be produced, the sulfonamide group proved to be too stable to convert into a sulfonic acid after reaction. The reactivity of 2-aminophenol was investigated to search for a new class of ion conducting polymer materials. Both the amine and the phenol groups are found to be reactive in a nucleophilic aromatic substitution, however not to the extent to allow the formation of high molecular weight polymer materials. Layer-by-layer films were assembled from aqueous solutions of poly(styrene sulfonate) and trimethylammonium functionalized poly(phenylene oxide). The deposition conditions were adjusted to increase the free charge carrier content, and chloride conductivites reached almost 30 mS/cm for the best films. Block and random poly(phenylene oxide) copolymers were produced from 2,6-dimethylphenol and 2,6-diphenylphenol and the methyl substituted repeat units were functionalized with trimethylammonium bromide. The block copolymers displayed bromide conductivities up to 26 mS/cm and outperformed the random copolymers, indicating that morphology has an effect on ion

  1. Polymer enrichment decelerates surfactant membranes near interfaces

    NASA Astrophysics Data System (ADS)

    Lipfert, F.; Frielinghaus, H.; Holderer, O.; Mattauch, S.; Monkenbusch, M.; Arend, N.; Richter, D.

    2014-04-01

    Close to a planar surface, lamellar structures are imposed upon otherwise bulk bicontinuous microemulsions. Thermally induced membrane undulations are modified by the presence of the rigid interface. While it has been shown that a pure membrane's dynamics are accelerated close to the interface, we observed nearly unchanged relaxation rates for membranes spiked with large amphiphilic diblock copolymers. An increase of the polymer concentration by a factor of 2-3 for the first and second surfactant membrane layers was observed. We interpret the reduced relaxation times as the result of an interplay between the bending rigidity and the characteristic distance of the first surfactant membrane to the rigid interface, which causes the hydrodynamic and steric interface effects described in Seifert's theory. The influence of these effects on decorated membranes yields a reduction of the frequencies and an amplification of the amplitudes of long-wavelength undulations, which are in accordance to our experimental findings.

  2. Poly(arlyene ether sulfone) based semi-interpenetrating polymer network membranes containing cross-linked poly(vinyl phosphonic acid) chains for fuel cell applications at high temperature and low humidity conditions

    NASA Astrophysics Data System (ADS)

    Kim, Kihyun; Heo, Pilwon; Ko, Taeyun; Kim, Ki-hyun; Kim, Sung-Kon; Pak, Chanho; Lee, Jong-Chan

    2015-10-01

    Semi-interpenetrating polymer network (semi-IPN) membranes are prepared by in-situ casting and thermal-initiated radical polymerization of vinyl phosphonic acid (VPA) and bis(2-(methacryloyloxy)ethyl) phosphate (BMAEP) in N,N-dimethylacetamide solutions of sulfonated poly(arylene ether sulfone) (SPAES). The incorporation of VPA units into the SPAES membranes improves proton conductivity especially at high temperature and low humidity conditions. In addition the cross-linker, BMAEP, prevents the decrease of the mechanical and chemical stabilities by the aliphatic linear poly(vinyl phosphonic acid) chains in the semi-IPN membranes, and furthermore the phosphonic acid group in BMAEP can prevent the decrease of the proton conductivity by the formation of cross-linked structures. Therefore, the resulting semi-IPN membranes show high proton conductivities up to 15 mS cm-1 at 120 °C and 40% RH. The fuel cell performance (187 mW cm-2 at 120 °C and 40% RH) of membrane-electrode assembly (MEA) from the semi-IPN membrane is found to be superior to that (145 mW cm-2 at 120 °C and 40% RH) of MEA from the SPAES membrane. The durability test result at the operating conditions indicates that the semi-IPN membrane is electrochemically very stable maintaining the low hydrogen cross-over and high power densities.

  3. Polymer networks: Modeling and applications

    NASA Astrophysics Data System (ADS)

    Masoud, Hassan

    Polymer networks are an important class of materials that are ubiquitously found in natural, biological, and man-made systems. The complex mesoscale structure of these soft materials has made it difficult for researchers to fully explore their properties. In this dissertation, we introduce a coarse-grained computational model for permanently cross-linked polymer networks than can properly capture common properties of these materials. We use this model to study several practical problems involving dry and solvated networks. Specifically, we analyze the permeability and diffusivity of polymer networks under mechanical deformations, we examine the release of encapsulated solutes from microgel capsules during volume transitions, and we explore the complex tribological behavior of elastomers. Our simulations reveal that the network transport properties are defined by the network porosity and by the degree of network anisotropy due to mechanical deformations. In particular, the permeability of mechanically deformed networks can be predicted based on the alignment of network filaments that is characterized by a second order orientation tensor. Moreover, our numerical calculations demonstrate that responsive microcapsules can be effectively utilized for steady and pulsatile release of encapsulated solutes. We show that swollen gel capsules allow steady, diffusive release of nanoparticles and polymer chains, whereas gel deswelling causes burst-like discharge of solutes driven by an outward flow of the solvent initially enclosed within a shrinking capsule. We further demonstrate that this hydrodynamic release can be regulated by introducing rigid microscopic rods in the capsule interior. We also probe the effects of velocity, temperature, and normal load on the sliding of elastomers on smooth and corrugated substrates. Our friction simulations predict a bell-shaped curve for the dependence of the friction coefficient on the sliding velocity. Our simulations also illustrate

  4. Model membranes grafted with long polymers

    NASA Astrophysics Data System (ADS)

    Nikolov, Vesselin Kirolov

    2004-06-01

    We study the effect on the elastic properties of lipid membranes induced by anchoring of long hydrophilic polymers. Theoretically, two limiting regimes for the membrane spontaneous curvature are expected : i) at low surface polymer concentration (mushroom regime) the spontaneous curvature should scale linearly with the surface density of anchored polymers; ii) at high coverage (brush regime) the dependence should be quadratic. We attempt to test the predictions for the brush regime by monitoring the morphological changes induced on giant vesicles. As long polymers we use fluorescently labeled λ-phage DNA molecules which are attached to biotinylated lipid vesicles with a biotin-avidin-biotin linkage. By varying the amount of biotinylated lipid in the membrane we control the surface concentration of the anchors. The amount of anchored DNA to the membrane is quantified with fluorescence measurements. Changes in the elastic properties of the membrane as DNA grafts to it are monitored via analysis of the vesicle fluctuations. The spontaneous curvature of the membrane increases as a function of the surface coverage. At higher grafting concentrations the vesicles bud. The size of the buds can also be used to assess the membrane curvature. The effect on the bending stiffness is a subject of further investigation. Wir untersuchen, welchen Einfluss die Verankerung von langen, hydrophilen Polymeren in Lipidmembranen auf deren elastische Eigenschaften ausübt. Theoretisch werden zwei Grenzbereiche für die spontane Krümmung der Membran erwartet: i) bei kleinen Oberflächenkonzentrationen des Polymers (Pilzgebiet) sollte die spontane Krümmung linear von der Oberflächendichte des verankerten Polymers abhängen; ii) bei hoher Bedeckung (Bürstengebiet) sollte die Abhängigkeit quadratisch sein. Wir versuchen, Vorhersagen für das Bürstengebiet zu prüfen, indem wir die morphologischen Veränderungen beobachten, die bei Riesen (Giant)- Vesikeln hervorgerufen werden. Als lange

  5. Water hydrogen bonding in proton exchange and neutral polymer membranes

    NASA Astrophysics Data System (ADS)

    Smedley, Sarah Black

    qualitative observations that can be made with pure D2O or H2O. The theory and experimental practice of determining the hydrogen bonding distribution of water in a range of proton exchange membranes bearing aromatic sulfonate and perfluorosulfonate groups using this OD stretch technique is discussed. To further understand how the acidity of the sulfonate can be altered and how the acidity affects the hydrogen bonding network of water in a polymer membrane, various polymers with small chemical differences in the perfluorosulfonate sidechain were studied. In addition to the vibrational spectroscopy measurements using HOD as a probe, the partial charges of the sulfonate groups were calculating using DMol3 DFT calculations. The calculations and the experimentally determined peak position of the OD stretch both correlated to give a ranking of acidity for the various sidechains. Three sulfonated poly(arylene sulfone) based polymers were studied using FTIR and DFT calculations to better understand how the acidity of the sulfonate groups were affected by the placement on the backbone. By increasing the number of sulfone groups, which have electron withdrawing properties, flanking the sulfonated aromatic ring, the acidity was increased. The charge density of a sulfonate group flanked by two sulfone groups was -1.626 (in units of fundamental charge), while the charge density of a sulfonate group flanked by one sulfone group increased to -1.703. Additionally, if the subsequent ring was unsulfonated, the charge density further increased to -1.737, indicating that some stability is gained by both available rings being sulfonated. The differences in charge density are reflected in the water uptake and conductivity measurements, where the samples with the lowest charge density had the highest water uptake and conductivity. The deconvoluted OD peak revealed that the sample with two sulfone groups flanking the sulfonated aromatic ring contains the highest amount of bulk-like water, which led

  6. Preparation of silica nanospheres and porous polymer membranes with controlled morphologies via nanophase separation

    PubMed Central

    2012-01-01

    We successfully synthesized two different structures, silica nanospheres and porous polymer membranes, via nanophase separation, based on a sol–gel process. Silica sol, which was in situ polymerized from tetraorthosilicate, was used as a precursor. Subsequently, it was mixed with a polymer that was used as a matrix component. It was observed that nanophase separation occurred after the mixing of polymer with silica sol and subsequent evaporation of solvents, resulting in organizing various structures, from random network silica structures to silica spheres. In particular, silica nanospheres were produced by manipulating the mixing ratio of polymer to silica sol. The size of silica beads was gradually changed from micro- to nanoscale, depending on the polymer content. At the same time, porous polymer membranes were generated by removing the silica component with hydrofluoric acid. Furthermore, porous carbon membranes were produced using carbon source polymer through the carbonization process. PMID:22873570

  7. Decoupling Mechanical and Ion Transport Properties in Polymer Electrolyte Membranes

    NASA Astrophysics Data System (ADS)

    McIntosh, Lucas D.

    Polymer electrolytes are mixtures of a polar polymer and salt, in which the polymer replaces small molecule solvents and provides a dielectric medium so that ions can dissociate and migrate under the influence of an external electric field. Beginning in the 1970s, research in polymer electrolytes has been primarily motivated by their promise to advance electrochemical energy storage and conversion devices, such as lithium ion batteries, flexible organic solar cells, and anhydrous fuel cells. In particular, polymer electrolyte membranes (PEMs) can improve both safety and energy density by eliminating small molecule, volatile solvents and enabling an all-solid-state design of electrochemical cells. The outstanding challenge in the field of polymer electrolytes is to maximize ionic conductivity while simultaneously addressing orthogonal mechanical properties, such as modulus, fracture toughness, or high temperature creep resistance. The crux of the challenge is that flexible, polar polymers best-suited for polymer electrolytes (e.g., poly(ethylene oxide)) offer little in the way of mechanical robustness. Similarly, polymers typically associated with superior mechanical performance (e.g., poly(methyl methacrylate)) slow ion transport due to their glassy polymer matrix. The design strategy is therefore to employ structured electrolytes that exhibit distinct conducting and mechanically robust phases on length scales of tens of nanometers. This thesis reports a remarkably simple, yet versatile synthetic strategy---termed polymerization-induced phase separation, or PIPS---to prepare PEMs exhibiting an unprecedented combination of both high conductivity and high modulus. This performance is enabled by co-continuous, isotropic networks of poly(ethylene oxide)/ionic liquid and highly crosslinked polystyrene. A suite of in situ, time-resolved experiments were performed to investigate the mechanism by which this network morphology forms, and it appears to be tied to the

  8. Network dynamics in nanofilled polymers

    NASA Astrophysics Data System (ADS)

    Baeza, Guilhem P.; Dessi, Claudia; Costanzo, Salvatore; Zhao, Dan; Gong, Shushan; Alegria, Angel; Colby, Ralph H.; Rubinstein, Michael; Vlassopoulos, Dimitris; Kumar, Sanat K.

    2016-04-01

    It is well accepted that adding nanoparticles (NPs) to polymer melts can result in significant property improvements. Here we focus on the causes of mechanical reinforcement and present rheological measurements on favourably interacting mixtures of spherical silica NPs and poly(2-vinylpyridine), complemented by several dynamic and structural probes. While the system dynamics are polymer-like with increased friction for low silica loadings, they turn network-like when the mean face-to-face separation between NPs becomes smaller than the entanglement tube diameter. Gel-like dynamics with a Williams-Landel-Ferry temperature dependence then result. This dependence turns particle dominated, that is, Arrhenius-like, when the silica loading increases to ~31 vol%, namely, when the average nearest distance between NP faces becomes comparable to the polymer's Kuhn length. Our results demonstrate that the flow properties of nanocomposites are complex and can be tuned via changes in filler loading, that is, the character of polymer bridges which `tie' NPs together into a network.

  9. Network dynamics in nanofilled polymers

    PubMed Central

    Baeza, Guilhem P.; Dessi, Claudia; Costanzo, Salvatore; Zhao, Dan; Gong, Shushan; Alegria, Angel; Colby, Ralph H.; Rubinstein, Michael; Vlassopoulos, Dimitris; Kumar, Sanat K.

    2016-01-01

    It is well accepted that adding nanoparticles (NPs) to polymer melts can result in significant property improvements. Here we focus on the causes of mechanical reinforcement and present rheological measurements on favourably interacting mixtures of spherical silica NPs and poly(2-vinylpyridine), complemented by several dynamic and structural probes. While the system dynamics are polymer-like with increased friction for low silica loadings, they turn network-like when the mean face-to-face separation between NPs becomes smaller than the entanglement tube diameter. Gel-like dynamics with a Williams–Landel–Ferry temperature dependence then result. This dependence turns particle dominated, that is, Arrhenius-like, when the silica loading increases to ∼31 vol%, namely, when the average nearest distance between NP faces becomes comparable to the polymer's Kuhn length. Our results demonstrate that the flow properties of nanocomposites are complex and can be tuned via changes in filler loading, that is, the character of polymer bridges which ‘tie' NPs together into a network. PMID:27109062

  10. Network dynamics in nanofilled polymers.

    PubMed

    Baeza, Guilhem P; Dessi, Claudia; Costanzo, Salvatore; Zhao, Dan; Gong, Shushan; Alegria, Angel; Colby, Ralph H; Rubinstein, Michael; Vlassopoulos, Dimitris; Kumar, Sanat K

    2016-01-01

    It is well accepted that adding nanoparticles (NPs) to polymer melts can result in significant property improvements. Here we focus on the causes of mechanical reinforcement and present rheological measurements on favourably interacting mixtures of spherical silica NPs and poly(2-vinylpyridine), complemented by several dynamic and structural probes. While the system dynamics are polymer-like with increased friction for low silica loadings, they turn network-like when the mean face-to-face separation between NPs becomes smaller than the entanglement tube diameter. Gel-like dynamics with a Williams-Landel-Ferry temperature dependence then result. This dependence turns particle dominated, that is, Arrhenius-like, when the silica loading increases to ∼31 vol%, namely, when the average nearest distance between NP faces becomes comparable to the polymer's Kuhn length. Our results demonstrate that the flow properties of nanocomposites are complex and can be tuned via changes in filler loading, that is, the character of polymer bridges which 'tie' NPs together into a network. PMID:27109062

  11. Water hydrogen bonding in proton exchange and neutral polymer membranes

    NASA Astrophysics Data System (ADS)

    Smedley, Sarah Black

    qualitative observations that can be made with pure D2O or H2O. The theory and experimental practice of determining the hydrogen bonding distribution of water in a range of proton exchange membranes bearing aromatic sulfonate and perfluorosulfonate groups using this OD stretch technique is discussed. To further understand how the acidity of the sulfonate can be altered and how the acidity affects the hydrogen bonding network of water in a polymer membrane, various polymers with small chemical differences in the perfluorosulfonate sidechain were studied. In addition to the vibrational spectroscopy measurements using HOD as a probe, the partial charges of the sulfonate groups were calculating using DMol3 DFT calculations. The calculations and the experimentally determined peak position of the OD stretch both correlated to give a ranking of acidity for the various sidechains. Three sulfonated poly(arylene sulfone) based polymers were studied using FTIR and DFT calculations to better understand how the acidity of the sulfonate groups were affected by the placement on the backbone. By increasing the number of sulfone groups, which have electron withdrawing properties, flanking the sulfonated aromatic ring, the acidity was increased. The charge density of a sulfonate group flanked by two sulfone groups was -1.626 (in units of fundamental charge), while the charge density of a sulfonate group flanked by one sulfone group increased to -1.703. Additionally, if the subsequent ring was unsulfonated, the charge density further increased to -1.737, indicating that some stability is gained by both available rings being sulfonated. The differences in charge density are reflected in the water uptake and conductivity measurements, where the samples with the lowest charge density had the highest water uptake and conductivity. The deconvoluted OD peak revealed that the sample with two sulfone groups flanking the sulfonated aromatic ring contains the highest amount of bulk-like water, which led

  12. Scale-dependent rigidity of polymer-ornamented membranes

    NASA Astrophysics Data System (ADS)

    Bickel, T.; Marques, C. M.

    2002-11-01

    We study the fluctuation spectrum of fluid membranes carrying grafted polymers. Contrary to usual descriptions, we find that the modifications induced by the polymers cannot be reduced to the renormalization of the membrane bending rigidity. Instead we show that the ornamented membrane exhibits a scale-dependent elastic modulus that we evaluate. In ornamented lamellar stacks, we further compute the polymer contribution to the Caillé parameter characterizing the power law singularities of the Bragg peaks.

  13. Self-Healing Polymer Networks

    NASA Astrophysics Data System (ADS)

    Tournilhac, Francois

    2012-02-01

    Supramolecular chemistry teaches us to control non-covalent interactions between organic molecules, particularly through the use of optimized building blocks able to establish several hydrogen bonds in parallel. This discipline has emerged as a powerful tool in the design of new materials through the concept of supramolecular polymers. One of the fascinating aspects of such materials is the possibility of controlling the structure, adding functionalities, adjusting the macroscopic properties of and taking profit of the non-trivial dynamics associated to the reversibility of H-bond links. Applications of these compounds may include adhesives, coatings, rheology additives, high performance materials, etc. However, the synthesis of such polymers at the industrial scale still remains a challenge. Our first ambition is to design supramolecular polymers with original properties, the second ambition is to devise simple and environmentally friendly methods for their industrial production. In our endeavours to create novel supramolecular networks with rubbery elasticity, self-healing ability and as little as possible creep, the strategy to prolongate the relaxation time and in the same time, keep the system flexible was to synthesize rather than a single molecule, an assembly of randomly branched H-bonding oligomers. We propose a strategy to obtain through a facile one-pot synthesis a large variety of supramolecular materials that can behave as differently as associating low-viscosity liquids, semi-crystalline or amorphous thermoplastics, viscoelastic melts or self-healing rubbers.

  14. Supramolecular polymer networks: hydrogels and bulk materials.

    PubMed

    Voorhaar, Lenny; Hoogenboom, Richard

    2016-07-21

    Supramolecular polymer networks are materials crosslinked by reversible supramolecular interactions, such as hydrogen bonding or electrostatic interactions. Supramolecular materials show very interesting and useful properties resulting from their dynamic nature, such as self-healing, stimuli-responsiveness and adaptability. Here we will discuss recent progress in polymer-based supramolecular networks for the formation of hydrogels and bulk materials. PMID:27206244

  15. Do Membranes Dream of Electric Tubes? Advanced Membranes Using Carbon Nanotube - Polymer Nanocomposites

    NASA Astrophysics Data System (ADS)

    de Lannoy, Charles-Francois Pedro Claude Karolek Ghislain

    Membrane technologies represent an energy efficient, effective solution for treating municipal and commercial waters/wastewaters. Membranes are predominantly polymer-based and despite steady advances in polymeric materials, they continue to suffer from operational problems including biofouling and breakages. This work addresses these two disparate problems by developing novel CNT-polymer nanocomposite materials that contain variously functionalized carbon nanotubes (fCNTs) in low quantities (<0.5wt%). Several strategies have been employed to achieve highly functional CNT-polymer nanocomposite membranes including blend mixing, ionic charge association, and covalent cross-linking with monomer and oligomer constituents. These CNT-polymer nanocomposite membranes were compared to traditional polymer membranes across various properties including increased Young's Modulus, changes in surface hydrophilicity, fine control over molecular weight cut-off and flux, and surface electrical conductivity. Membranes with high surface electrical conductivity were further tested for their anti-biofouling properties. Finally, CNT stability and polymer compatibility were evaluated throughout membrane manufacture, use, and cleaning. The incorporation of CNTs mixed in bulk phase and linked through ionic associations in polymer matrices showed significant (50%) increases in Young's modulus for certain CNT functionalizations and derivatization percent. Membranes formed with high surface electrical conductivity demonstrated almost complete resistance to biofouling (> 95%) in long-term bacterially challenged experiments. CNTs and polymer mixtures that lacked covalent or ionic bonds were susceptible to significant (up to 10%) loss of CNTs during membrane non-solvent gelation and aggressive chemical cleaning treatment. Functionalized carbon nanotubes endow polymer membranes with their unique strength and electrically conductive properties. These added properties were demonstrated to greatly

  16. Biodegradable polymer membrane used as septal splint.

    PubMed

    Watzinger, F; Wutzl, A; Wanschitz, F; Ewers, R; Turhani, D; Seemann, R

    2008-05-01

    The treatment of a crooked nose is one of the most challenging rhinoplastic procedures. Correction of the abnormally curved or fractured septum has been reported using mostly scoring techniques, septoplasty and submucous resection techniques; cartilaginous spreader grafts can also be sutured to the distorted septum. Extracorporal septal straightening and repositioning/refixation is another useful but difficult technique. A common problem of septal cartilaginous grafting techniques is to harvest enough straight cartilage to correct the deformity. (Other donor sites such as rib cartilage are used, but harvesting additional cartilage is a time-consuming procedure and carries the risk of donor site morbidity.) Recent studies have been published using alloplastic internal splinting of the deformed septum. The use of poly p-dioxanone foils and porous polyethylene has been suggested before. In this study, a novel grafting material, a PolyMax membrane that has potential advantages over both materials, is presented. This is a porous biodegradable polymer made out of 70:30 poly(L-lactide-co-D,L-lactide) that remains stable for at least 7 months. Poly p-dioxanone loses its stability after only 2 months, whereas porous polyethylene is a permeable material that is controversial due to possible complications in cases of membrane exposure and infection. In this preliminary report the PolyMax membrane was used successfully in 3 patients. PMID:18337063

  17. Solid polymer electrolyte composite membrane comprising laser micromachined porous support

    DOEpatents

    Liu, Han; LaConti, Anthony B.; Mittelsteadt, Cortney K.; McCallum, Thomas J.

    2011-01-11

    A solid polymer electrolyte composite membrane and method of manufacturing the same. According to one embodiment, the composite membrane comprises a rigid, non-electrically-conducting support, the support preferably being a sheet of polyimide having a thickness of about 7.5 to 15 microns. The support has a plurality of cylindrical pores extending perpendicularly between opposing top and bottom surfaces of the support. The pores, which preferably have a diameter of about 5 microns, are made by laser micromachining and preferably are arranged in a defined pattern, for example, with fewer pores located in areas of high membrane stress and more pores located in areas of low membrane stress. The pores are filled with a first solid polymer electrolyte, such as a perfluorosulfonic acid (PFSA) polymer. A second solid polymer electrolyte, which may be the same as or different than the first solid polymer electrolyte, may be deposited over the top and/or bottom of the first solid polymer electrolyte.

  18. Building polymer fiber optic network

    NASA Astrophysics Data System (ADS)

    Bienias, P.; Bereś-Pawlik, E.

    2015-09-01

    The paper describes an investigation of transmission in LAN with using polymer optical fiber (POF). There were used two kinds of POF, step index plastic optical fiber (SI-POF) and graded index plastic optical fiber (GI-POF). Furthermore, the paper include a comparison between SI-POF and GI-POF and possibilities of using them. For the project's needs, new type of couplers has been designed and built, optimization has been performed to obtain the best parameters for designed couplers. Additionally, the coupler has been built from the same material, which GI-POF - PMMA is made of. Moreover, CWDM (Coarse Wavelength Division Multiplexing) transmissions is investigated to improve the network capacity.

  19. Interaction of multiple biomimetic antimicrobial polymers with model bacterial membranes

    NASA Astrophysics Data System (ADS)

    Baul, Upayan; Kuroda, Kenichi; Vemparala, Satyavani

    2014-08-01

    Using atomistic molecular dynamics simulations, interaction of multiple synthetic random copolymers based on methacrylates on prototypical bacterial membranes is investigated. The simulations show that the cationic polymers form a micellar aggregate in water phase and the aggregate, when interacting with the bacterial membrane, induces clustering of oppositely charged anionic lipid molecules to form clusters and enhances ordering of lipid chains. The model bacterial membrane, consequently, develops lateral inhomogeneity in membrane thickness profile compared to polymer-free system. The individual polymers in the aggregate are released into the bacterial membrane in a phased manner and the simulations suggest that the most probable location of the partitioned polymers is near the 1-palmitoyl-2-oleoyl-phosphatidylglycerol (POPG) clusters. The partitioned polymers preferentially adopt facially amphiphilic conformations at lipid-water interface, despite lacking intrinsic secondary structures such as α-helix or β-sheet found in naturally occurring antimicrobial peptides.

  20. Interaction of multiple biomimetic antimicrobial polymers with model bacterial membranes

    SciTech Connect

    Baul, Upayan Vemparala, Satyavani; Kuroda, Kenichi

    2014-08-28

    Using atomistic molecular dynamics simulations, interaction of multiple synthetic random copolymers based on methacrylates on prototypical bacterial membranes is investigated. The simulations show that the cationic polymers form a micellar aggregate in water phase and the aggregate, when interacting with the bacterial membrane, induces clustering of oppositely charged anionic lipid molecules to form clusters and enhances ordering of lipid chains. The model bacterial membrane, consequently, develops lateral inhomogeneity in membrane thickness profile compared to polymer-free system. The individual polymers in the aggregate are released into the bacterial membrane in a phased manner and the simulations suggest that the most probable location of the partitioned polymers is near the 1-palmitoyl-2-oleoyl-phosphatidylglycerol (POPG) clusters. The partitioned polymers preferentially adopt facially amphiphilic conformations at lipid-water interface, despite lacking intrinsic secondary structures such as α-helix or β-sheet found in naturally occurring antimicrobial peptides.

  1. Red-green-blue laser emission from cascaded polymer membranes.

    PubMed

    Zhai, Tianrui; Wang, Yonglu; Chen, Li; Wu, Xiaofeng; Li, Songtao; Zhang, Xinping

    2015-12-21

    Red-green-blue polymer laser emission is achieved in a free-standing membrane device consisting of three distributed feedback cavities. The polymer membrane is fabricated via interference lithography and a simple lift-off process. Multilayer structures can be assembled by cascading several polymer membranes. Thus optically pumped, simultaneous, red-green-blue laser emission is obtained from a three-layer cascaded membrane structure. This simple and low-cost fabrication technique can be used for compact, integrated laser sources. PMID:26580128

  2. Dynamics of a polymer chain confined in a membrane.

    PubMed

    Ramachandran, S; Komura, S; Seki, K; Gompper, G

    2011-05-01

    We present a Brownian dynamics theory with full hydrodynamics (Stokesian dynamics) for a Gaussian polymer chain embedded in a liquid membrane which is surrounded by bulk solvent and walls. The mobility tensors are derived in Fourier space for the two geometries, namely, a free membrane embedded in a bulk fluid, and a membrane sandwiched by the two walls. Within the preaveraging approximation, a new expression for the diffusion coefficient of the polymer is obtained for the free-membrane geometry. We also carry out a Rouse normal mode analysis to obtain the relaxation time and the dynamical structure factor. For large polymer size, both quantities show Zimm-like behavior in the free-membrane case, whereas they are Rouse-like for the sandwiched membrane geometry. We use the scaling argument to discuss the effect of excluded-volume interactions on the polymer relaxation time. PMID:21562968

  3. Red-green-blue laser emission from cascaded polymer membranes

    NASA Astrophysics Data System (ADS)

    Zhai, Tianrui; Wang, Yonglu; Chen, Li; Wu, Xiaofeng; Li, Songtao; Zhang, Xinping

    2015-11-01

    Red-green-blue polymer laser emission is achieved in a free-standing membrane device consisting of three distributed feedback cavities. The polymer membrane is fabricated via interference lithography and a simple lift-off process. Multilayer structures can be assembled by cascading several polymer membranes. Thus optically pumped, simultaneous, red-green-blue laser emission is obtained from a three-layer cascaded membrane structure. This simple and low-cost fabrication technique can be used for compact, integrated laser sources.Red-green-blue polymer laser emission is achieved in a free-standing membrane device consisting of three distributed feedback cavities. The polymer membrane is fabricated via interference lithography and a simple lift-off process. Multilayer structures can be assembled by cascading several polymer membranes. Thus optically pumped, simultaneous, red-green-blue laser emission is obtained from a three-layer cascaded membrane structure. This simple and low-cost fabrication technique can be used for compact, integrated laser sources. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr05965h

  4. Universal Cyclic Topology in Polymer Networks.

    PubMed

    Wang, Rui; Alexander-Katz, Alfredo; Johnson, Jeremiah A; Olsen, Bradley D

    2016-05-01

    Polymer networks invariably possess topological defects: loops of different orders which have profound effects on network properties. Here, we demonstrate that all cyclic topologies are a universal function of a single dimensionless parameter characterizing the conditions for network formation. The theory is in excellent agreement with both experimental measurements of hydrogel loop fractions and Monte Carlo simulations without any fitting parameters. We demonstrate the superposition of the dilution effect and chain-length effect on loop formation. The one-to-one correspondence between the network topology and primary loop fraction demonstrates that the entire network topology is characterized by measurement of just primary loops, a single chain topological feature. Different cyclic defects cannot vary independently, in contrast to the intuition that the densities of all topological species are freely adjustable. Quantifying these defects facilitates studying the correlations between the topology and properties of polymer networks, providing a key step in overcoming an outstanding challenge in polymer physics. PMID:27203346

  5. Universal Cyclic Topology in Polymer Networks

    NASA Astrophysics Data System (ADS)

    Wang, Rui; Alexander-Katz, Alfredo; Johnson, Jeremiah A.; Olsen, Bradley D.

    2016-05-01

    Polymer networks invariably possess topological defects: loops of different orders which have profound effects on network properties. Here, we demonstrate that all cyclic topologies are a universal function of a single dimensionless parameter characterizing the conditions for network formation. The theory is in excellent agreement with both experimental measurements of hydrogel loop fractions and Monte Carlo simulations without any fitting parameters. We demonstrate the superposition of the dilution effect and chain-length effect on loop formation. The one-to-one correspondence between the network topology and primary loop fraction demonstrates that the entire network topology is characterized by measurement of just primary loops, a single chain topological feature. Different cyclic defects cannot vary independently, in contrast to the intuition that the densities of all topological species are freely adjustable. Quantifying these defects facilitates studying the correlations between the topology and properties of polymer networks, providing a key step in overcoming an outstanding challenge in polymer physics.

  6. Computer Simulations of Ion Transport in Polymer Electrolyte Membranes.

    PubMed

    Mogurampelly, Santosh; Borodin, Oleg; Ganesan, Venkat

    2016-06-01

    Understanding the mechanisms and optimizing ion transport in polymer membranes have been the subject of active research for more than three decades. We present an overview of the progress and challenges involved with the modeling and simulation aspects of the ion transport properties of polymer membranes. We are concerned mainly with atomistic and coarser level simulation studies and discuss some salient work in the context of pure binary and single ion conducting polymer electrolytes, polymer nanocomposites, block copolymers, and ionic liquid-based hybrid electrolytes. We conclude with an outlook highlighting future directions. PMID:27070764

  7. Conducting polymer supported bilayer lipid membrane reconstituted with alamethicin

    NASA Astrophysics Data System (ADS)

    Zhang, Hao; Salinas, Sergio; Baba Sundaresan, Vishnu

    2011-09-01

    Ionic electroactive polymers and bioderived materials have been independently demonstrated as actuators, sensors and energy harvesting devices. In an electroactive polymer, the applied electric field between the cathode and anode drives ion transport between the electrodes, impregnated electrolyte and the bulk of the polymer to generate force and displacement. Similarly, in a bioderived material an input stimulus (electrical, chemoelectrical or chemical) applied across the protein in a bilayer lipid membrane (BLM) displaces ions across the membrane barrier and enables sensing and actuation functions. This paper presents a novel architecture for a device that integrates the ionic function of an electroactive polymer and a bioderived material into a thin-film laminated device combining their unique advantages. A conducting polymer (PPy(DBS)) is used as the electroactive polymer and alamethicin-bound bilayer lipid membrane is used as the bioderived material in the thin-film laminated device. Owing to the configuration of the laminated device, the protein regulates the ionic concentration in the conducting polymer and regulates the electrochemical doping/undoping process in the polymer. By electrically connecting the conducting polymer across its thickness, this arrangement provides a mechanism external to the polymer besides electrical field that can control the electrical, mechanical and/or optical properties of the conducting polymer. This paper also presents the fabrication and characterization of the integrated ionic device and presents a template for the development of a novel category of electroactive ionic devices.

  8. Charged Polymer Membranes for Environmental/Energy Applications.

    PubMed

    Kamcev, Jovan; Freeman, Benny D

    2016-06-01

    Ion exchange membranes are used in various membrane-based processes (e.g., electrodialysis, fuel cells). Charged solute transport is largely governed by the charged groups on the polymer backbone. In this review, fundamental relationships describing salt permeability and ionic conductivity, as well as water permeability, in charged polymers are developed within the framework of the Nernst-Planck and solution-diffusion models. The influence of fixed charge groups and polymer structure on water sorption and diffusion is discussed. Current understanding of ion partitioning in charged polymers, focusing on the use of thermodynamic models (i.e., Donnan theory) to describe such phenomena, is summarized. Ion diffusivity data from the literature are interpreted using a model developed by Mackie and Meares to assess relative and absolute effects of the polymer and fixed charge groups on ion diffusivity. Furthermore, membrane requirements for several important technologies are listed. Knowledge gaps and opportunities for fundamental research are also discussed. PMID:26979410

  9. Method for dialysis on microchips using thin porous polymer membrane

    DOEpatents

    Singh, Anup K.; Kirby, Brian J.; Shepodd, Timothy J.

    2009-05-19

    Laser-induced phase-separation polymerization of a porous acrylate polymer is used for in-situ fabrication of dialysis membranes inside glass microchannels. A shaped 355 nm laser beam is used to produce a porous polymer membrane with a thickness of about 15 .mu.m, which bonds to the glass microchannel and forms a semi-permeable membrane. Differential permeation through a membrane formed with pentaerythritol triacrylate was observed and quantified by comparing the response of the membrane to fluorescein and fluorescently tagging 200 nm latex microspheres. Differential permeation was observed and quantified by comparing the response to rhodamine 560 and lactalbumin protein in a membrane formed with SPE-methylene bisacrylamide. The porous membranes illustrate the capability for the present technique to integrate sample cleanup into chip-based analysis systems.

  10. Dialysis on microchips using thin porous polymer membranes

    DOEpatents

    Singh, Anup K.; Kirby, Brian J.; Shepodd, Timothy J.

    2007-09-04

    Laser-induced phase-separation polymerization of a porous acrylate polymer is used for in-situ fabrication of dialysis membranes inside glass microchannels. A shaped 355 nm laser beam is used to produce a porous polymer membrane with a thickness of about 15 .mu.m, which bonds to the glass microchannel and form a semi-permeable membrane. Differential permeation through a membrane formed with pentaerythritol triacrylate was observed and quantified by comparing the response of the membrane to fluorescein and fluorescently tagging 200 nm latex microspheres. Differential permeation was observed and quantified by comparing the response to rhodamine 560 and lactalbumin protein in a membrane formed with SPE-methylene bisacrylamide. The porous membranes illustrate the capability for the present technique to integrate sample cleanup into chip-based analysis systems.

  11. Nanoscale glucan polymer network causes pathogen resistance

    PubMed Central

    Eggert, Dennis; Naumann, Marcel; Reimer, Rudolph; Voigt, Christian A.

    2014-01-01

    Successful defence of plants against colonisation by fungal pathogens depends on the ability to prevent initial penetration of the plant cell wall. Here we report that the pathogen-induced (1,3)-β-glucan cell wall polymer callose, which is deposited at sites of attempted penetration, directly interacts with the most prominent cell wall polymer, the (1,4)-β-glucan cellulose, to form a three-dimensional network at sites of attempted fungal penetration. Localisation microscopy, a super-resolution microscopy technique based on the precise localisation of single fluorescent molecules, facilitated discrimination between single polymer fibrils in this network. Overexpression of the pathogen-induced callose synthase PMR4 in the model plant Arabidopsis thaliana not only enlarged focal callose deposition and polymer network formation but also resulted in the exposition of a callose layer on the surface of the pre-existing cellulosic cell wall facing the invading pathogen. The importance of this previously unknown polymeric defence network is to prevent cell wall hydrolysis and penetration by the fungus. We anticipate our study to promote nanoscale analysis of plant-microbe interactions with a special focus on polymer rearrangements in and at the cell wall. Moreover, the general applicability of localisation microscopy in visualising polymers beyond plant research will help elucidate their biological function in complex networks. PMID:24561766

  12. Bioinspired polymer vesicles and membranes for biological and medical applications.

    PubMed

    Palivan, Cornelia G; Goers, Roland; Najer, Adrian; Zhang, Xiaoyan; Car, Anja; Meier, Wolfgang

    2016-01-21

    Biological membranes play an essential role in living organisms by providing stable and functional compartments, preserving cell architecture, whilst supporting signalling and selective transport that are mediated by a variety of proteins embedded in the membrane. However, mimicking cell membranes - to be applied in artificial systems - is very challenging because of the vast complexity of biological structures. In this respect a highly promising strategy to designing multifunctional hybrid materials/systems is to combine biological molecules with polymer membranes or to design membranes with intrinsic stimuli-responsive properties. Here we present supramolecular polymer assemblies resulting from self-assembly of mostly amphiphilic copolymers either as 3D compartments (polymersomes, PICsomes, peptosomes), or as planar membranes (free-standing films, solid-supported membranes, membrane-mimetic brushes). In a bioinspired strategy, such synthetic assemblies decorated with biomolecules by insertion/encapsulation/attachment, serve for development of multifunctional systems. In addition, when the assemblies are stimuli-responsive, their architecture and properties change in the presence of stimuli, and release a cargo or allow "on demand" a specific in situ reaction. Relevant examples are included for an overview of bioinspired polymer compartments with nanometre sizes and membranes as candidates in applications ranging from drug delivery systems, up to artificial organelles, or active surfaces. Both the advantages of using polymer supramolecular assemblies and their present limitations are included to serve as a basis for future improvements. PMID:26563574

  13. Swelling molecular entanglement networks in polymer glasses.

    PubMed

    McGraw, Joshua D; Dalnoki-Veress, Kari

    2010-08-01

    Entanglements in a polymer network are like knots between the polymer chains, and they are at the root of many phenomena observed in polymer systems. When a polymer glass is strained, cracklike deformations called crazes may be formed and the study of these regions can reveal much about the nature of entanglements. We have studied crazes in systems that are blends of long polymer chains diluted with chains of various small molecular weights. The range of diluting chain lengths is such that a fraction of them have conformations leading to entanglements. It has been found that a system with more short chains added acts like one in which the entanglement density is smaller than that in an undiluted system. We propose a model that quantitatively predicts the density of effective entanglements of a polydisperse system of polymer chains which is consistent with our experimental data. PMID:20866829

  14. Composite membranes from photochemical synthesis of ultrathin polymer films

    NASA Astrophysics Data System (ADS)

    Liu, Chao; Martin, Charles R.

    1991-07-01

    THERE has recently been a resurgence of interest in synthetic membranes and membrane-based processes1-12. This is motivated by a wide variety of technological applications, such as chemical separations1-7, bioreactors and sensors8,9, energy conversion10,11 and drug-delivery systems12. Many of these technologies require the ability to prepare extremely thin, defect-free synthetic (generally polymeric) films, which are supported on microporous supports to form composite membranes. Here we describe a method for producing composite membranes of this sort that incorporate high-quality polymer films less than 50-nm thick. The method involves interfacial photopolymerization of a thin polymer film on the surface of the microporous substrate. We have been able to use this technique to synthesize a variety of functionalized ultrathin films based on electroactive, photoactive and ion-exchange polymers. We demonstrate the method here with composite membranes that show exceptional gas-transport properties.

  15. Flexible solid polymer electrolyte membran formed by photopolymerization

    NASA Astrophysics Data System (ADS)

    Cao, Jinwei; Kyu, Thein

    2014-03-01

    Binary and ternary phase diagrams of poly(ethylene glycol) dimethacrylate (PEGDMA,succinonitrile(SCN), and bis(trifluoromethane)sulfonimide (LiTFSI) blends have been established to provide guidance to fabricationof polymer electrolyte membrane (PEM). The phase diagram of binary PEGDMA/SCN mixture is of a typical eutectic typ, whereas the binary PEGDMA/LiTFSI mixture reveals a eutectic trend exhibiting a wide single phase region at intermediate composition. Likewise, the ternary phase diagram of PEGDMA/SCN/LiTFSI mixture shows a wide isotropic regio. The PEM network, formed by UV-crosslinking of PEGDMA in the isotropic region, is a solid amorphous network, but flexible and stretchable. Ion conductivity of PEMwas measured as a function of temperature at different ratios of PEGDMA/SCN and SCN/LiTFSI. Of particular importance is that these PEM networks possessvery high roo-temperature ion conductivity on the order of 10-3 S cm-1, which reaches the level of 10-2 S cm-1 at elevated temperatures of 60-70 °C. The electrochemical stability of the solid PEM will be evaluated by cyclic voltammetry and its potential applicabilityinflexible lithium ion battery will be discussed.

  16. Interfacial welding of dynamic covalent network polymers

    NASA Astrophysics Data System (ADS)

    Yu, Kai; Shi, Qian; Li, Hao; Jabour, John; Yang, Hua; Dunn, Martin L.; Wang, Tiejun; Qi, H. Jerry

    2016-09-01

    Dynamic covalent network (or covalent adaptable network) polymers can rearrange their macromolecular chain network by bond exchange reactions (BERs) where an active unit replaces a unit in an existing bond to form a new bond. Such macromolecular events, when they occur in large amounts, can attribute to unusual properties that are not seen in conventional covalent network polymers, such as shape reforming and surface welding; the latter further enables the important attributes of material malleability and powder-based reprocessing. In this paper, a multiscale modeling framework is developed to study the surface welding of thermally induced dynamic covalent network polymers. At the macromolecular network level, a lattice model is developed to describe the chain density evolution across the interface and its connection to bulk stress relaxation due to BERs. The chain density evolution rule is then fed into a continuum level interfacial model that takes into account surface roughness and applied pressure to predict the effective elastic modulus and interfacial fracture energy of welded polymers. The model yields particularly accessible results where the moduli and interfacial strength of the welded samples as a function of temperature and pressure can be predicted with four parameters, three of which can be measured directly. The model identifies the dependency of surface welding efficiency on the applied thermal and mechanical fields: the pressure will affect the real contact area under the consideration of surface roughness of dynamic covalent network polymers; the chain density increment on the real contact area of interface is only dependent on the welding time and temperature. The modeling approach shows good agreement with experiments and can be extended to other types of dynamic covalent network polymers using different stimuli for BERs, such as light and moisture etc.

  17. Polymer electrolyte membranes with exceptional conductivity anisotropy via holographic polymerization

    NASA Astrophysics Data System (ADS)

    Smith, Derrick M.; Cheng, Shan; Wang, Wenda; Bunning, Timothy J.; Li, Christopher Y.

    2014-12-01

    Polymer electrolyte membranes using an ionic liquid as electrolyte with an ionic conductivity anisotropy of ∼5000 have been fabricated using a holographic polymerization nanomanufacturing technique. The resultant structure is referred to as holographic polymer electrolyte membranes (hPEMs), which are comprised of alternating nanolayers of a room temperature ionic liquid and crosslinked polymer resin, confirmed under TEM imaging. These hPEMs also show no reduction in room temperature conductivity with respect to the loaded ionic liquid when characterized in the plane of ionic liquid nanolayers. At elevated temperatures with the optimal electrolyte volume loading, calculation shows that the free ion concentration is higher than the pure ionic liquid, suggesting that the photopolymer dual-functionalizes as a loadbearing scaffold and an ion-complexing agent, allowing for more ions to participate in charge transfer. These hPEMs provide a promising solution to decoupling mechanical enhancement and ion transport in polymer electrolyte membranes.

  18. Modeling heterogeneous polymer-grafted nanoparticle networks

    NASA Astrophysics Data System (ADS)

    Zhang, Tao; Mbanga, Badel; Yashin, Victor; Balazs, Anna

    Via a dynamic 3D computational approach, we simulate the heterogeneous polymer-grafted nanoparticle networks. The nanoparticles rigid cores are decorated with a corona of grafted polymers, which contain reactive functional groups at the chain ends. With the overlap of grafted polymers, these reactive groups can form weak labile bonds, which can reform after breakage, or stronger bonds, which rupture irreversibly and thus, the nanoparticles are interconnected by dual cross-links. Previous work has been done on homogeneous networks, while we introduce the heterogeneity by considering two types of particles having different reactive functional groups, so that the labile bond energy varies depending on types of the two end reactive groups. We study the effect of tensile and rotational deformations on the network morphology, and observe, in particular, the phase separation of two types of particles. Our results will provide guidelines for designing transformable material that can controllably change structure under mechanical action.

  19. The influence of the membrane-polymer interface on colloidal membrane dynamics and phase behavior

    NASA Astrophysics Data System (ADS)

    Zakhary, Mark J.

    A primary challenge in the field of self-assembly is to identify simple interactions that produce well-defined, complex, and controllable materials. A large part of this task is to creatively engineer appropriate assembly components with such suitable interactions built-in. Here, we demonstrate that rod-like subunits, experimentally modeled by fd bacteriophage viruses, with simple and predictable hard-core repulsive interactions, exhibit a great wealth of fascinating self-assembly behavior. These rods form two-dimensional liquid crystalline colloidal membranes consisting of monolayers of aligned particles owing purely to entropic considerations. Due to surface tension, rods near the edge of the monolayers twist, resulting in an elastic nematic ring surrounding the fluid-like membrane interior, and it is the rich phenomena rooted in the interplay between the edge and the interior that is the subject of this thesis. The chiral nature of the fd subunits causes a symmetry breaking at the membrane edge, which leads to chiral control of interfacial tension and resultantly a controllable, reversible morphological transition between membranes and one-dimensional twisted ribbons. Using optical microscopic and optical tweezer techniques, we show that a nucleation barrier exists in association with the membrane-ribbon transition, and investigate this barrier using fluctuation analysis as well as highly controlled force-extension experiments. The finite bending rigidity of the membrane edge is studied, and we show that long filamentous polymers spontaneously adhere to the edge, introducing the concept of geometrical edge-active agents. By analyzing the suppressed edge fluctuations of filament-bound membranes, it is found that the edge bending rigidity varies by up to an order of magnitude in a predictable and controllable way. Finally, we study the effect of the monolayer edge on the membrane coalescence, and observe two types of stable liquid crystalline defects that form at

  20. Solid polymer electrolyte composite membrane comprising plasma etched porous support

    DOEpatents

    Liu, Han; LaConti, Anthony B.

    2010-10-05

    A solid polymer electrolyte composite membrane and method of manufacturing the same. According to one embodiment, the composite membrane comprises a rigid, non-electrically-conducting support, the support preferably being a sheet of polyimide having a thickness of about 7.5 to 15 microns. The support has a plurality of cylindrical pores extending perpendicularly between opposing top and bottom surfaces of the support. The pores, which preferably have a diameter of about 0.1 to 5 microns, are made by plasma etching and preferably are arranged in a defined pattern, for example, with fewer pores located in areas of high membrane stress and more pores located in areas of low membrane stress. The pores are filled with a first solid polymer electrolyte, such as a perfluorosulfonic acid (PFSA) polymer. A second solid polymer electrolyte, which may be the same as or different than the first solid polymer electrolyte, may be deposited over the top and/or bottom of the first solid polymer electrolyte.

  1. Deformation propagation in responsive polymer network films

    NASA Astrophysics Data System (ADS)

    Ghosh, Surya K.; Cherstvy, Andrey G.; Metzler, Ralf

    2014-08-01

    We study the elastic deformations in a cross-linked polymer network film triggered by the binding of submicron particles with a sticky surface, mimicking the interactions of viral pathogens with thin films of stimulus-responsive polymeric materials such as hydrogels. From extensive Langevin Dynamics simulations we quantify how far the network deformations propagate depending on the elasticity parameters of the network and the adhesion strength of the particles. We examine the dynamics of the collective area shrinkage of the network and obtain some simple relations for the associated characteristic decay lengths. A detailed analysis elucidates how the elastic energy of the network is distributed between stretching and compression modes in response to the particle binding. We also examine the force-distance curves of the repulsion or attraction interactions for a pair of sticky particles in the polymer network film as a function of the particle-particle separation. The results of this computational study provide new insight into collective phenomena in soft polymer network films and may, in particular, be applied to applications for visual detection of pathogens such as viruses via a macroscopic response of thin films of cross-linked hydrogels.

  2. Polymer electrolyte membrane assembly for fuel cells

    NASA Technical Reports Server (NTRS)

    Yen, Shiao-Ping S. (Inventor); Kindler, Andrew (Inventor); Yavrouian, Andre (Inventor); Halpert, Gerald (Inventor)

    2002-01-01

    An electrolyte membrane for use in a fuel cell can contain sulfonated polyphenylether sulfones. The membrane can contain a first sulfonated polyphenylether sulfone and a second sulfonated polyphenylether sulfone, wherein the first sulfonated polyphenylether and the second sulfonated polyphenylether sulfone have equivalent weights greater than about 560, and the first sulfonated polyphenylether and the second sulfonated polyphenylether sulfone also have different equivalent weights. Also, a membrane for use in a fuel cell can contain a sulfonated polyphenylether sulfone and an unsulfonated polyphenylether sulfone. Methods for manufacturing a membrane electrode assemblies for use in fuel cells can include roughening a membrane surface. Electrodes and methods for fabricating such electrodes for use in a chemical fuel cell can include sintering an electrode. Such membranes and electrodes can be assembled into chemical fuel cells.

  3. Polymer electrolyte membrane assembly for fuel cells

    NASA Technical Reports Server (NTRS)

    Yen, Shiao-Ping S. (Inventor); Kindler, Andrew (Inventor); Yavrouian, Andre (Inventor); Halpert, Gerald (Inventor)

    2000-01-01

    An electrolyte membrane for use in a fuel cell can contain sulfonated polyphenylether sulfones. The membrane can contain a first sulfonated polyphenylether sulfone and a second sulfonated polyphenylether sulfone, wherein the first sulfonated polyphenylether and the second sulfonated polyphenylether sulfone have equivalent weights greater than about 560, and the first sulfonated polyphenylether and the second sulfonated polyphenylether sulfone also have different equivalent weights. Also, a membrane for use in a fuel cell can contain a sulfonated polyphenylether sulfone and an unsulfonated polyphenylether sulfone. Methods for manufacturing a membrane electrode assemblies for use in fuel cells can include roughening a membrane surface. Electrodes and methods for fabricating such electrodes for use in a chemical fuel cell can include sintering an electrode. Such membranes and electrodes can be assembled into chemical fuel cells.

  4. Inorganic polymer-derived ceramic membranes

    SciTech Connect

    Brinker, C.J.; Sehgal, R.; Raman, N.; Schunk, P.R.; Headley, T.J.

    1993-12-31

    Polymeric silica sols were used to prepare membranes on commercial {gamma}-A1{sub 2}O{sub 3} supports. Aging of the silica sols was shown to be effective to form discrete membrane layers. He/N{sub 2} selectivity factors exceeding ideal Knudsen values were observed when the sols were prepared under conditions in which the condensation rate was minimized. It is proposed that the average pore size of the membrane depends on the balance of capillary pressure and modulus during membrane deposition and that the breadth of the pore size distribution might be influenced by the extent of condensation accompanying membrane deposition. The use of organic templates may allow independent control of pore size, pore shape, and pore volume. The membranes are to be used in processing natural gas (gas separation/purification).

  5. Research Trends in Polymer Electrolyte Membranes for PEMFC

    NASA Astrophysics Data System (ADS)

    Zaidi, S. M. Javaid

    In this chapter research trends followed by various scientific groups for the development of polymeric membranes have been described and reviewed. Most notably, the developments made at Ballard Advanced Materials (BAM) and some of their results are discussed. In general three different approaches have been followed worldwide by various research groups for the development and conception of alternative membranes. These approaches include: (1) modifying perfluorinated ionomer membranes; (2) functionalization of aromatic hydrocarbon polymers/ membranes; and (3) composite membranes based on solid inorganic proton conducting materials and the organic polymer matrix or prepare acid-base blends and their composite to improve their water retention properties. The current trend is for the composite and hybrid membranes, which combines the properties of both the polymeric component and inorganic part. The most widely studied polymer after Nafion is the sulfonated polyether-ether ketone (SPEEK), as it has a high potential for commercialization. A number of research projects are currently undergoing dealing with the SPEEK polymer in various research labs.

  6. Estimation of intermolecular interactions in polymer networks

    SciTech Connect

    Subrananian, P.R.; Galiatsatos, V.

    1993-12-31

    Strain-birefringence measurements have been used to estimate intermolecular interactions in polymer networks. The intensity of the interaction has been quantified through a theoretical scheme recently proposed by Erman. The results show that these interactions diminish with decreasing molecular weight between cross-links and decreasing cross-link functionality.

  7. A novel method for producing microspheres with semipermeable polymer membranes

    NASA Technical Reports Server (NTRS)

    Lin, K. C.; Wang, Taylor G.

    1992-01-01

    A new and systematic approach for producing polymer microspheres has been demonstrated. The membrane of the microsphere is formed by immersing the polyanionic droplet into a collapsing annular sheet, which is made of another polycation polymer solution. This method minimizes the impact force during the time when the chemical reaction takes place, hence eliminating the shortcomings of the current encapsulation techniques. The results of this study show the feasibility of this method for mass production of microcapsules.

  8. Ultra fast polymer network blue phase liquid crystals

    NASA Astrophysics Data System (ADS)

    Hussain, Zakir; Masutani, Akira; Danner, David; Pleis, Frank; Hollfelder, Nadine; Nelles, Gabriele; Kilickiran, Pinar

    2011-06-01

    Polymer-stabilization of blue phase liquid crystal systems within a host polymer network are reported, which enables ultrafast switching flexible displays. Our newly developed method to stabilize the blue phase in an existing polymer network (e.g., that of a polymer network liquid crystal; PNLC) has shown wide temperature stability and fast response speeds. Systems where the blue phase is stabilized in an already existing polymer network are attractive candidates for ultrafast LCDs. The technology also promises to be applied to flexible PNLC and/or polymer dispersed liquid crystal (PDLC) displays using plastic substrate such as polyethylene terephthalate (PET).

  9. Robust Polymer Composite Membranes for Hydrogen Separation

    SciTech Connect

    2009-11-01

    This factsheet describes a research project whose primary goal is to achieve a major improvement in the combined economics and performance of polymenzimidazole-based (PBI) membrane technology in the application of hydrogen separation from a syngas stream.

  10. Thermoelectric Potential of Polymer-Scaffolded Ionic Liquid Membranes

    NASA Astrophysics Data System (ADS)

    Datta, R. S.; Said, S. M.; Sahamir, S. R.; Karim, M. R.; Sabri, M. F. M.; Nakajo, T.; Kubouchi, M.; Hayashi, K.; Miyazaki, Y.

    2014-06-01

    Organic thin films have been viewed as potential thermoelectric (TE) materials, given their ease of fabrication, flexibility, cost effectiveness, and low thermal conductivity. However, their intrinsically low electrical conductivity is a main drawback which results in a relatively lower TE figure of merit for polymer-based TE materials than for inorganic materials. In this paper, a technique to enhance the ion transport properties of polymers through the introduction of ionic liquids is presented. The polymer is in the form of a nanofiber scaffold produced using the electrospinning technique. These fibers were then soaked in different ionic liquids based on substituted imidazolium such as 1-ethyl-3-methylimidazolium chloride or 1-butyl-3-methylimidazolium bromide. This method was applied to electrospun polyacrylonitrile and a mixture of polyvinyl alcohol and chitosan polymers. The ion transport properties of the membranes have been observed to increase with increasing concentration of ionic liquid, with maximum electrical conductivity of 1.20 × 10-1 S/cm measured at room temperature. Interestingly, the maximum electrical conductivity value surpassed the value of pure ionic liquids. These results indicate that it is possible to significantly improve the electrical conductivity of a polymer membrane through a simple and cost-effective method. This may in turn boost the TE figures of merit of polymer materials, which are well known to be considerably lower than those of inorganic materials. Results in terms of the Seebeck coefficient of the membranes are also presented in this paper to provide an overall representation of the TE potential of the polymer-scaffolded ionic liquid membranes.

  11. Towards the construction of synthetic protocells: Engineering responsive polymer membranes

    NASA Astrophysics Data System (ADS)

    Kamat, Neha Prashant

    Polymersomes are vesicles formed through self-assembly of diblock copolymers that display the lamellar structure of cellular membranes. The work described in this thesis has been driven by the long-range goal of creating a polymersome protocell; a polymer vesicle, that carries out some life activities, such as signaling, communication, sensation or growth. We developed three different areas important for cellular mimicry, and used the concept of inter-particle communication as a model behavior to guide the design parameters of our system. These parameters include designing responsive membranes, controlling membrane architecture and composition, and controlling vesicle spatial position. First, we created responsive polymer membranes that use an optical illumination to trigger and report membrane response. Confocal microscopy and micropipette aspiration were used to show that polymer membranes that contained a porphyrin-based chromophore could be induced to deform and rupture in response to light when a luminal solute, dextran, was encapsulated. This response could be tuned by changing the molecular weight of dextran and the membrane polymer. We then showed how supermolecular porphyrin-based fluorophores can be used as sensors for membrane stress. We showed that changes in porphyrin emission report changes in membrane tension by using fluorimetry, a multispectral camera and aspiration techniques to characterize changes in the optical emission of these near infrared (NIR) emissive probes embedded within the hydrophobic core of the polymersome membrane. Next, we constructed polymersomes with increased control over the membrane diameter, membrane composition, and luminal encapsulates using microfluidics. Using micropipette aspiration, we verified the unilamellarity of fluid membranes consisting of PEO30-b-PBD46 diblock copolymers. In addition, we used micropipette aspiration to both track and verify solvent removal from double emulsion-templated polymersomes. Finally

  12. Modification of chitosan membranes with nanosilica particles as polymer electrolyte membranes

    NASA Astrophysics Data System (ADS)

    Kusumastuti, Ella; Siniwi, Widasari Trisna; Mahatmanti, F. Widhi; Jumaeri, Atmaja, Lukman; Widiastuti, Nurul

    2016-04-01

    Chitosan has been widely used as polymer matrix for Polymer Electrolyte Membrane (PEM) application replacing Nafion which has shortcomings in terms of high methanol permeability that degrades the performance of fuel cells. Chitosan membranes modification is performed by adding nanosilica to prevent methanol transport through the membrane. Nanosilica is synthesized by sol-gel method and the particle diameter is obtained by analysis using Breunner Emmet Teller (BET) that is 6.59 nm. Nanosilica is mixed with chitosan solution to obtain nanosilica-chitosan as polymer electrolyte membrane. The membranes are synthesized through phase inversion method with nanosilica composition including 0; 0.5; 1; 2; 3; 5; and 10% w/w of chitosan. Characterization of the membranes indicate that the results of water swelling, proton conductivity and methanol permeability of the membrane with 3% nanosilica respectively were 49.23%, 0.231 S/cm, and 5.43 x 10-7 cm2/s. Based on the results of membrane selectivity calculation, the optimum membrane is the composition of 3% nanosilica with value 5.91 x 105 S s cm-3. The results of functional groups analysis with FTIR showed that it was only physical interaction that occurred between chitosan and nanosilica since no significant changes found in peak around the wave number 1000-1250 cm--1.

  13. Highly Conductive, Stretchable, and Transparent Solid Polymer Electrolyte Membrane

    NASA Astrophysics Data System (ADS)

    He, Ruixuan; Echeverri, Mauricio; Kyu, Thein

    2014-03-01

    With the guidance of ternary phase diagrams, completely amorphous polymer electrolyte membranes (PEM) were successfully prepared by melt processing for lithium-ion battery. The PEM under consideration consisted of poly (ethylene glycol diacrylate) (PEGDA), succinonitrile (SCN) and Lithium bis(trifluoro-methane)sulfonamide (LiTFSI). After UV-crosslinking, the PEM is transparent and light-weight. Addition of SCN plastic crystal affords not only dissociation of the lithium salt, but also plasticization to the crosslinked PEGDA network. Of particular importance is the achievement of room-temperature ionic conductivity of ~10-3 S/cm, which is comparable to that of commercial liquid electrolyte. Higher ionic conductivities were achieved at elevated temperatures or with use of a moderately higher molecular weight of PEGDA. In terms of electrochemical and chemical stability, the PEM exhibited oxidative stability up to 5 V against lithium reference electrode. Stable interface behavior between the PEM and lithium electrode is also seen with ageing time. In the tensile tests, samples containing low molecular weight PEGDA are stiffer, whereas the high molecular weight PEGDA is stretchable up to 80% elongation. Supported by NSF-DMR 1161070.

  14. Fundamental and Applied Studies of Polymer Membranes

    NASA Astrophysics Data System (ADS)

    Imbrogno, Joseph

    Four major areas have been studied in this research: 1) synthesizing novel monomers, e.g. chiral monomers, to produce new types of functionalized membranes for the biotechnology and pharmaceutical industries, 2) hydrophobic brush membranes for desalinating brackish water, sea water, and separating organics, 3) fundamental studies of water interactions at surfaces using sum frequency generation (SFG), and 4) discovering new surface chemistries that will control the growth and differentiation of stem cells. We have developed a novel synthesis method in order to increase the breadth of our high throughput screening library. This library was generated using maleimide chemistry to react a common methacrylate linker with a variety of different functions groups (R groups) in order to form new monomers that were grafted from the surface of PES ultrafiltration membranes. From this work, we discovered that the chirality of a membrane can affect performance when separating chiral feed streams. This effect was observed when filtering bovine serum albumin (BSA) and ovalbumin in a high salt phosphate buffered saline (PBS, 150 mM salt). The Phe grafted membranes showed a large difference in performance when filtering BSA with selectivity of 1.13 and 1.00 for (S) and (R) Phe, respectively. However, when filtering ovalbumin, the (S) and (R) modified surfaces showed selectivity of 2.06 and 2.31, respectively. The higher selectivity enantiomer switched for the two different proteins. Permeability when filtering BSA was 3.06 LMH kPa-1 and 4.31 LMH kPa -1 for (S)- and (R)- Phe, respectively, and 2.65 LMH kPa -1 and 2.10 LMH kPa-1 when filtering ovalbumin for (S)- and (R)- Phe, respectively. Additionally, these effects were no longer present when using a low salt phosphate buffer (PB, 10 mM salt). Since, to our knowledge, membrane chirality is not considered in current industrial systems, this discovery could have a large impact on the pharmaceutical and biotechnology industries. We

  15. Fundamental and Applied Studies of Polymer Membranes

    NASA Astrophysics Data System (ADS)

    Imbrogno, Joseph

    Four major areas have been studied in this research: 1) synthesizing novel monomers, e.g. chiral monomers, to produce new types of functionalized membranes for the biotechnology and pharmaceutical industries, 2) hydrophobic brush membranes for desalinating brackish water, sea water, and separating organics, 3) fundamental studies of water interactions at surfaces using sum frequency generation (SFG), and 4) discovering new surface chemistries that will control the growth and differentiation of stem cells. We have developed a novel synthesis method in order to increase the breadth of our high throughput screening library. This library was generated using maleimide chemistry to react a common methacrylate linker with a variety of different functions groups (R groups) in order to form new monomers that were grafted from the surface of PES ultrafiltration membranes. From this work, we discovered that the chirality of a membrane can affect performance when separating chiral feed streams. This effect was observed when filtering bovine serum albumin (BSA) and ovalbumin in a high salt phosphate buffered saline (PBS, 150 mM salt). The Phe grafted membranes showed a large difference in performance when filtering BSA with selectivity of 1.13 and 1.00 for (S) and (R) Phe, respectively. However, when filtering ovalbumin, the (S) and (R) modified surfaces showed selectivity of 2.06 and 2.31, respectively. The higher selectivity enantiomer switched for the two different proteins. Permeability when filtering BSA was 3.06 LMH kPa-1 and 4.31 LMH kPa -1 for (S)- and (R)- Phe, respectively, and 2.65 LMH kPa -1 and 2.10 LMH kPa-1 when filtering ovalbumin for (S)- and (R)- Phe, respectively. Additionally, these effects were no longer present when using a low salt phosphate buffer (PB, 10 mM salt). Since, to our knowledge, membrane chirality is not considered in current industrial systems, this discovery could have a large impact on the pharmaceutical and biotechnology industries. We

  16. Electropolymerization on wireless electrodes towards conducting polymer microfibre networks

    NASA Astrophysics Data System (ADS)

    Koizumi, Yuki; Shida, Naoki; Ohira, Masato; Nishiyama, Hiroki; Tomita, Ikuyoshi; Inagi, Shinsuke

    2016-01-01

    Conducting polymers can be easily obtained by electrochemical oxidation of aromatic monomers on an electrode surface as a film state. To prepare conducting polymer fibres by electropolymerization, templates such as porous membranes are necessary in the conventional methods. Here we report the electropolymerization of 3,4-ethylenedioxythiophene and its derivatives by alternating current (AC)-bipolar electrolysis. Poly(3,4-ethylenedioxythiophene) (PEDOT) derivatives were found to propagate as a fibre form from the ends of Au wires used as bipolar electrodes (BPEs) parallel to an external electric field, without the use of templates. The effects of applied frequency and of the solvent on the morphology, growth rate and degree of branching of these PEDOT fibres were investigated. In addition, a chain-growth model for the formation of conductive material networks was also demonstrated.

  17. Electropolymerization on wireless electrodes towards conducting polymer microfibre networks

    PubMed Central

    Koizumi, Yuki; Shida, Naoki; Ohira, Masato; Nishiyama, Hiroki; Tomita, Ikuyoshi; Inagi, Shinsuke

    2016-01-01

    Conducting polymers can be easily obtained by electrochemical oxidation of aromatic monomers on an electrode surface as a film state. To prepare conducting polymer fibres by electropolymerization, templates such as porous membranes are necessary in the conventional methods. Here we report the electropolymerization of 3,4-ethylenedioxythiophene and its derivatives by alternating current (AC)-bipolar electrolysis. Poly(3,4-ethylenedioxythiophene) (PEDOT) derivatives were found to propagate as a fibre form from the ends of Au wires used as bipolar electrodes (BPEs) parallel to an external electric field, without the use of templates. The effects of applied frequency and of the solvent on the morphology, growth rate and degree of branching of these PEDOT fibres were investigated. In addition, a chain-growth model for the formation of conductive material networks was also demonstrated. PMID:26804140

  18. Humidification studies on polymer electrolyte membrane fuel cell

    NASA Astrophysics Data System (ADS)

    Sridhar, P.; Perumal, Ramkumar; Rajalakshmi, N.; Raja, M.; Dhathathreyan, K. S.

    Two methods of humidifying the anode gas, namely, external and membrane humidification, for a polymer electrolyte membrane fuel (PEMFC) cell are explained. It is found that the water of solvation of protons decreases with increase in the current density and the electrode area. This is due to insufficient external humidification. In a membrane-based humidification, an optimum set of parameters, such as gas flow rate, area and type of the membrane, must be chosen to achieve effective humidification. The present study examines the dependence of water pick-up by hydrogen on the temperature, area and thickness of the membrane in membrane humidification. Since the performance of the fuel cell is dependent more on hydrogen humidification than on oxygen humidification, the scope of the work is restricted to the humidification of hydrogen using Nafion ® membrane. An examination is made on the dependence of water pick-up by hydrogen in membrane humidification on the temperature, area and thickness of the membrane. The dependence of fuel cell performance on membrane humidification and external humidification in the anode gas is also considered.

  19. Polymer single crystal membrane from liquid/liquid interface

    NASA Astrophysics Data System (ADS)

    Wang, Wenda; Li, Christopher; Soft Matter Research Group-Drexel University Team

    2013-03-01

    Vesicles, mimicking the structure of cell membrane at the molecular scale, are small membrane-enclosed sacks that can store or transport substances. The weak mechanical properties and the nature of environment-sensitivity of the current available vesicles: liposomes, polymersomes, colloidsomes limit their applications as an excellent candidate for targeting delivery of drugs/genes in biomedical engineering and treatment. Recently, we developed an emulsion-based method to grow curved polymer single crystals. Varying the polymer concentration and/or the emulsification conditions (such as surfactant concentration, water-oil volume ratio), curved crystals with different sizes and different openness could be obtained. This growing process was attributed to polymer crystal growth along the liquid/liquid interface. In addition, the liquid/liquid interfacial crystal growth is promising for synthesis of enclosed hollow sphere.

  20. Multichannel taste sensors with lipid, lipid like polymer membranes

    NASA Astrophysics Data System (ADS)

    Szpakowska, M.; Szwacki, J.; Marjańska, E.

    2008-08-01

    The elaboration of a sensitive taste sensor for discrimination of different soft drinks is very important in food industry. The short review of taste sensors described in the literature is presented. Two types of potentiometric taste sensors, one with lipophilic compound-polymer membranes (ISE) and the other with lipid polymer membrane and a conducting polymer film (All solid state electrode, ASSE) were tested in appropriate taste solutions. Five channel ISE sensor was examined in acid, sour and sweet solutions. This sensor was sensitive to bitter and sour substances and not too sensitive to sucrose concentration. It was successfully used for discrimination of different kind of soft drinks. Four channel ASSE sensor was examined in sour solutions. It was found that stability and sensitivity of ASSE are lower than ISE. Therefore, it seems that the previous one cannot be applied in taste sensor.

  1. Mechanisms of gas permeation through polymer membranes

    SciTech Connect

    Stern, S.A.

    1992-01-01

    Progress is reported in two areas: (1) Concentration-temperature superposition principle (CTSP). CTSP is a theoretical model for describing the gas solubility in glassy polymers swollen by the penetrant gas. It has been extended to describe the dependence of gas diffusivity and permeability on penetrant pressure. Further extension to diffusion of gas mixtures is being studied. (2)Solubility of gases in poly(alkyl methacrylates). Solubility of methane in poly(ethyl methacrylate) and poly(n-butyl methacrylate) was measured; the Langmuir capacity constant was found to not reflect a lower excess free volume; an equation is given for relating the constant to the glass transition temperature. Solubility of ethane in the latter polymer is affected by plasticization.

  2. New interpenetrating network type siloxane polymer electrolyte.

    SciTech Connect

    Oh, B.; Hyung, Y.-E.; Vissers, D. R.; Amine, K.; Chemical Engineering

    2002-11-01

    An interpenetrating network (IPN), comb-type, siloxane-based solid polymer electrolyte solid polymer electrolyte was prepared and its electrochemical properties were evaluated. The cross-linking reaction conditions were established from accelerated rate calorimetry studies. An IPN solid ploymer electrolyte with 60 wt % of the comb-shaped siloxane showed an ionic conductivity of greater than 5x10{sup -4} S/cm at 37 C, with a wide electrochemical stability window of up to 4.5 V vs. lithium. A Li metal/solid polymer electrolyte/LiNi{sub 0.8}Co{sub 0.2}O{sub 2} cell showed promising discharge capacities above 130 mAh/g and good cycling performance.

  3. Dynamic assembly of polymer nanotube networks via kinesin powered microtubule filaments

    NASA Astrophysics Data System (ADS)

    Paxton, Walter F.; Bouxsein, Nathan F.; Henderson, Ian M.; Gomez, Andrew; Bachand, George D.

    2015-06-01

    We describe for the first time how biological nanomotors may be used to actively self-assemble mesoscale networks composed of diblock copolymer nanotubes. The collective force generated by multiple kinesin nanomotors acting on a microtubule filament is large enough to overcome the energy barrier required to extract nanotubes from polymer vesicles comprised of poly(ethylene oxide-b-butadiene) in spite of the higher force requirements relative to extracting nanotubes from lipid vesicles. Nevertheless, large-scale polymer networks were dynamically assembled by the motors. These networks displayed enhanced robustness, persisting more than 24 h post-assembly (compared to 4-5 h for corresponding lipid networks). The transport of materials in and on the polymer membranes differs substantially from the transport on analogous lipid networks. Specifically, our data suggest that polymer mobility in nanotubular structures is considerably different from planar or 3D structures, and is stunted by 1D confinement of the polymer subunits. Moreover, quantum dots adsorbed onto polymer nanotubes are completely immobile, which is related to this 1D confinement effect and is in stark contrast to the highly fluid transport observed on lipid tubules.We describe for the first time how biological nanomotors may be used to actively self-assemble mesoscale networks composed of diblock copolymer nanotubes. The collective force generated by multiple kinesin nanomotors acting on a microtubule filament is large enough to overcome the energy barrier required to extract nanotubes from polymer vesicles comprised of poly(ethylene oxide-b-butadiene) in spite of the higher force requirements relative to extracting nanotubes from lipid vesicles. Nevertheless, large-scale polymer networks were dynamically assembled by the motors. These networks displayed enhanced robustness, persisting more than 24 h post-assembly (compared to 4-5 h for corresponding lipid networks). The transport of materials in and on

  4. Biomimetic oral mucin from polymer micelle networks

    NASA Astrophysics Data System (ADS)

    Authimoolam, Sundar Prasanth

    -functional implant coats. KEYWORDS: Biomimic, Bioapplication, Drug delivery, Filomicelle, Mucin, Polymer networks.

  5. Modeling aligning effect of polymer network in polymer stabilized nematic liquid crystals

    NASA Astrophysics Data System (ADS)

    Yang, Deng-Ke; Cui, Yue; Nemati, Hossein; Zhou, Xiaochen; Moheghi, Alireza

    2013-12-01

    We developed a phenomenological theory to describe the aligning field of polymer networks in polymer stabilized liquid crystals where sub-micron size polymer networks are phase separated from the liquid crystal in dispersion. The polymer networks are anisotropic and anchor the liquid crystals in their longitudinal direction. They inhibit the liquid crystals reorientation when external stimuli, such as electric field and temperature, are applied and reduce the relaxation time from distorted states. We model the effects produced by the polymer networks as an effective aligning field. We calculate the effective field as a function of the polymer network volume fraction and the lateral size of the network. The theory is compared with experimental results and good agreements were obtained. It is very useful in predicting how much polymer networks change the driving voltage and response time of liquid crystal devices.

  6. Filament networks attached to membranes: cytoskeletal pressure and local bilayer deformation

    NASA Astrophysics Data System (ADS)

    Auth, Thorsten; Safran, S. A.; Gov, Nir S.

    2007-11-01

    Several cell types, among them red blood cells, have a cortical, two-dimensional (2D) network of filaments sparsely attached to their lipid bilayer. In many mammalian cells, this 2D polymer network is connected to an underlying 3D, more rigid cytoskeleton. In this paper, we consider the pressure exerted by the thermally fluctuating, cortical network of filaments on the bilayer and predict the bilayer deformations that are induced by this pressure. We treat the filaments as flexible polymers and calculate the pressure that a network of such linear chains exerts on the bilayer; we then minimize the bilayer shape in order to predict the resulting local deformations. We compare our predictions with membrane deformations observed in electron micrographs of red blood cells. The polymer pressure along with the resulting membrane deformation can lead to compartmentalization, regulate in-plane diffusion and may influence protein sorting as well as transmit signals to the polymerization of the underlying 3D cytoskeleton.

  7. Cell-Culture Reactor Having a Porous Organic Polymer Membrane

    NASA Technical Reports Server (NTRS)

    Koontz, Steven L. (Inventor)

    2000-01-01

    A method for making a biocompatible polymer article using a uniform atomic oxygen treatment is disclosed. The substrate may be subsequently optionally grated with a compatibilizing compound. Compatibilizing compounds may include proteins, phosphory1choline groups, platelet adhesion preventing polymers, albumin adhesion promoters, and the like. The compatibilized substrate may also have a living cell layer adhered thereto. The atomic oxygen is preferably produced by a flowing afterglow microwave discharge, wherein the substrate resides in a sidearm out of the plasma. Also, methods for culturing cells for various purposes using the various membranes are disclosed as well. Also disclosed are porous organic polymers having a distributed pore chemistry (DPC) comprising hydrophilic and hydrophobic regions, and a method for making the DPC by exposing the polymer to atomic oxygen wherein the rate of hydrophilization is greater than the rate of mass loss.

  8. Polybenzimidazole-multiwall carbon nanotubes composite membranes for polymer electrolyte membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Guerrero Moreno, Nayibe; Gervasio, Dominic; Godínez García, Andrés; Pérez Robles, Juan Francisco

    2015-12-01

    Polymer membranes are prepared as a composite of polybenzimidazole and non-functionalized multiwall carbon nanotubes (PBI-CNT) and polybenzimidazole (PBI) only. Each is doped with H3PO4 (PA) and used as a proton exchange membrane (PEM) as the electrolyte in a fuel cell. The proton conductivities at 180 °C for the doped PBI membrane (PBIPA) and the doped PBI-CNT membrane (PBICNTPA) are 6.3 × 10-2 and 7.4 × 10-2 Scm-1 respectively. A single fuel cell having these membranes as electrolyte has a Pt catalyzed hydrogen gas fed anode and a similar oxygen cathode without humidification of feed gases; the cell with the PBICNTPA membrane has higher open circuit voltage (0.96 V) than that with a PBIPA membrane (0.8 V) at 180 °C. The mechanical stability of the membrane improves with CNTs addition. The tensile strength of the composite PBI-CNT membrane with 1 wt.% CNTs loading is 32% higher and the Young's Modulus is 147% higher than the values for a membrane of PBI alone. The improvement in conductivity and mechanical properties in the composite membrane due to the CNT addition indicates that a PBI-CNT membrane is a good alternative as a membrane electrolyte in a PEMFC.

  9. Transport in Polymer-Electrolyte Membranes I. Physical Model

    SciTech Connect

    Weber, Adam Z.; Newman, John

    2003-06-02

    In this paper, a physical model is developed that is semiphenomenological and takes into account Schroeder's paradox. Using the wealth of knowledge contained in the literature regarding polymer-electrolyte membranes as a basis, a novel approach is taken in tying together all of the data into a single coherent theory. This approach involves describing the structural changes of the membrane due to water content, and casting this in terms of capillary phenomena. By treating the membrane in this fashion, Schroeder's paradox can be elucidated. Along with the structural changes, two different transport mechanisms are presented and discussed. These mechanisms, along with the membrane's structural changes, comprise the complete physical model of the membrane. The model is shown to agree qualitatively with different membranes and different membrane forms, and is applicable to modeling perfluorinated sulfonic acid and similar membranes. It is also the first physically based comprehensive model of transport in a membrane that includes a physical description of Schroeder's paradox, and it bridges the gap between the two types of macroscopic models currently in the literature.

  10. NanoCapillary Network Proton Conducting Membranes for High Temperature Hydrogen/Air Fuel Cells

    SciTech Connect

    Pintauro, Peter

    2012-07-09

    The objective of this proposal is to fabricate and characterize a new class of NanoCapillary Network (NCN) proton conducting membranes for hydrogen/air fuel cells that operate under high temperature, low humidity conditions. The membranes will be intelligently designed, where a high density interconnecting 3-D network of nm-diameter electrospun proton conducting polymer fibers is embedded in an inert (uncharged) water/gas impermeable polymer matrix. The high density of fibers in the resulting mat and the high ion-exchange capacity of the fiber polymer will ensure high proton conductivity. To further enhance water retention, molecular silica will be added to the sulfonated polymer fibers. The uncharged matrix material will control water swelling of the high ion-exchange capacity proton conducting polymer fibers and will impart toughness to the final nanocapillary composite membrane. Thus, unlike other fuel cell membranes, the role of the polymer support matrix will be decoupled from that of the proton-conducting channels. The expected final outcome of this 5-year project is the fabrication of fuel cell membranes with properties that exceed the DOE’s technical targets, in particular a proton conductivity of 0.1 S/cm at a temperature less than or equal to120°C and 25-50% relative humidity.

  11. Interfacial Effects in Polymer Membranes for Clean Energy

    NASA Astrophysics Data System (ADS)

    Soles, Christopher

    2013-03-01

    Polymeric membranes are critical components in several emerging clean energy technologies. Examples include proton exchange membranes for hydrogen fuel cells, anion exchange membranes for alkaline fuel cells, flow batteries, and even block copolymer membranes for solid electrolytes/separators in lithium ion and other battery technologies. In all of these examples the function of the membrane is to physically separate two reactive electrodes or reactants, but allow the transport or exchange of specific ions through the membrane between the active electrodes. The flow of the charged ionic species between the electrodes can be used to balance the flow of electrons through an external electrical circuit that connects the electrodes, thereby storing or delivering charge electrochemically. In this presentation I will review the use of polymeric membranes in electrochemical energy storage technologies and discuss the critical issues related to the membranes that hinder these technologies. In particular I will also focus on the role the polymer membrane interface on device performance. At some point the polymer membrane must be interfaced with an active electrode or catalyst and the nature of this interface can significantly impact performance. Simulations of device performance based on bulk membrane transport properties often fail to predict the actual performance and empirical interfacial impedance terms usually added to capture the device performance. In this presentation I will explore the origins of this interfacial impedance in the different types of fuel cell membranes (proton and alkaline) by creating model thin film membranes where all of the membrane can be considered interfacial. We then use these thin films as a surrogate for the interfacial regions of a bulk membrane and then quantify the structure, dynamics, and transport properties of water and ions in the confined interfacial films. Using neutron reflectivity, grazing incidence X-ray diffraction, and

  12. Decoupling ion flux and mechanical strength in polymer battery membranes

    NASA Astrophysics Data System (ADS)

    Smith, Derrick; Cheng, Shan; Bunning, Timothy; Li, Christopher

    2013-03-01

    While much research has demonstrated repeatable characteristics of electrolyte membranes, the fundamentals behind the interactions during ionic diffusion in solid polymer electrolyte membranes for battery applications are not well understood, specifically the role of nanostructures, which hold the key to improving performance of energy storage devices such as fuel cells and Lithium ion batteries. The challenges in fabricating highly controlled model systems are largely responsible for the interdependent ambiguities between nanostructures and the corresponding ion transport behavior. In this work, Holographic Polymer Electrolyte Membrane (hPEM) volume gratings comprised of alternating layers of cross-linked polymer resin and ionic liquid were fabricated using holographic polymerization with an average d-spacing of 180 nm. These one-dimensional confinement structures were used to quantitatively study the anisotropic ionic conductivity properties, and correlate this behavior to nano-confinement and phase mixing. These membranes provide a platform in decoupling ion flux and bulk mechanical properties for future blend systems for battery applications. These volume gratings also offer an exciting route to fabricate multifunctional gratings for optic and sensing applications.

  13. Polymer membranes as separators for supercapacitors

    NASA Astrophysics Data System (ADS)

    Szubzda, Bronisław; Szmaja, Aleksandra; Ozimek, Mariusz; Mazurkiewicz, Sławomir

    2014-12-01

    The purpose of the studies described was to examine the influence of low-energy plasma modification of polyamide and polypropylene polymer nonwoven fabrics on the usable properties of supercapacitors when using these fabrics as the separator material. To achieve this goal the following investigations were carried out: testing the time required for electrolyte saturation of separators and the conductivity of the electrolyte contained in the separator, as well as electrochemical examinations of supercapacitor models in which the modified fabric separators were used. The tests conducted fully confirm the usability of this modification for cleaning the surface and improving the wettability of separators by the electrolyte, which in turn results in a significant decrease of the internal resistance of the supercapacitor, thus increasing the usable power of the device.

  14. Water and polymer dynamics in highly crosslinked polyamide membranes

    NASA Astrophysics Data System (ADS)

    Frieberg, Bradley; Chan, Edwin; Tyagi, Madhu; Stafford, Christopher; Soles, Christopher

    Highly crosslinked polyamides for reverse osmosis are the state-of-the-art active material in membranes for desalination. The thin film composite membrane structure that is used commercially has been empirically designed to selectively allow the passage of water molecules and minimize the passage of solutes such as salt. However, due to the large roughness and variability of the polyamide layer, there is a limited understanding of the structure-property relationship for these materials as well as the transport mechanism. To better understand the water transport mechanism we measure the water and polymer dynamics of polyamide membranes using quasi-elastic neutron scattering (QENS). By hydrating the membrane with deuterated water, we are able to isolate the dynamics of the hydrogenated membrane on the pico- and nanosecond time scales. By subsequently hydrating the membranes with hydrogenated water, the QENS measurements on the same times scales reveal information about both the translational and rotational dynamics of water confined within the polyamide membrane. Further understanding of the water diffusion mechanism will establish design rules in which the performance of future membrane materials can be improved.

  15. A Polymer Membrane Containing Fe0 as a Contaminant Barrier

    SciTech Connect

    Shimotori, Tsutomu; Nuxoll, Eric E.; Cussler, Edward L.; Arnold, William A.

    2003-11-03

    A polyvinyl alcohol (PVA) membrane containing iron (Fe0) particles was developed and tested as a model barrier for contaminant containment. Carbon tetrachloride, copper (Cu2+), nitrobenzene, 4-nitroacetophenone, and chromate (CrO4 2-) were selected as model contaminants. Compared with a pure PVA membrane, the Fe0/PVA membrane can increase the breakthrough lag time for Cu2+ and carbon tetrachloride by more than 100 fold. The increase in the lag time was smaller for nitrobenzene and 4-nitroacetophenone which stoichiometrically require more iron and for which the PVA membrane has a higher permeability. The effect of Fe0 was even smaller for CrO4 2- because of its slow reaction. Forty-five percent of the iron, based on the content in the dry membrane prior to hydration, was consumed by reaction with Cu2+ and 19% by reaction with carbon tetrachloride. Similarly, 25%, 17%, and 6% of the iron was consumed by nitrobenzene, 4-nitroacetophenone, and CrO4 2-, respectively. These percentages approximately double when the loss of iron during membrane hydration is considered. The permeability of the Fe0/PVA membrane after breakthrough was within a factor of three for that of pure PVA, consistent with theory. These results suggest that polymer membranes with embedded Fe0 have potential as practical contaminant barriers.

  16. Highly conductive polymer electrolyte membranes modified with polyethylene glycol-bis-carbamate

    NASA Astrophysics Data System (ADS)

    Fu, Guopeng; Dempsey, Janel; Kyu, Thein

    By virtue of its non-flammability and chemical stability, polyethylene glycol (PEG) networks have shown potential application in all solid-state polymer electrolyte membranes (PEM). However, room temperature ionic conductivity of these PEG based PEMs is inherently low. Plasticization of these PEMs is needed to improve the ionic conductivity. It was demonstrated by this group that small-molecule plasticizers such as succinonitrile, ethylene carbonate, or urea-carbamate can boost ionic conductivity of solid-state polymer electrolyte membranes. Polyethylene glycol bis-carbamate (PEGBC) was synthesized via condensation reaction of polyethylene glycol diamine and ethylene carbonate. The PEGBC modified PEM has shown higher ionic conductivity relative to the unmodified PEM. Moreover, PEGBC modified PEM has a better thermal stability relative to ethylene carbonate based liquid electrolyte with enhanced ionic conductivity. Supported by NSF-DMR 1161070, 1502543 and REU 1359321.

  17. Layered conductive polymer on nylon membrane templates for high performance, thin-film supercapacitor electrodes

    NASA Astrophysics Data System (ADS)

    Shi, HaoTian Harvey; Naguib, Hani E.

    2016-04-01

    Flexible Thin-film Electrochemical Capacitors (ECs) are emerging technology that plays an important role as energy supply for various electronics system for both present era and the future. Intrinsically conductive polymers (ICPs) are promising pseudo-capacitive materials as they feature both good electrical conductivity and high specific capacitance. This study focuses on the construction and characterization of ultra-high surface area porous electrodes based on coating of nano-sized conductive polymer materials on nylon membrane templates. Herein, a novel nano-engineered electrode material based on nylon membranes was presented, which allows the creation of super-capacitor devices that is capable of delivering competitive performance, while maintaining desirable mechanical characteristics. With the formation of a highly conductive network with the polyaniline nano-layer, the electrical conductivity was also increased dramatically to facilitate the charge transfer process. Cyclic voltammetry and specific capacitance results showed promising application of this type of composite materials for future smart textile applications.

  18. A review of radiation-grafted polymer electrolyte membranes for alkaline polymer electrolyte membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Zhou, Tianchi; Shao, Rong; Chen, Song; He, Xuemei; Qiao, Jinli; Zhang, Jiujun

    2015-10-01

    The past two decades have witnessed many efforts to develop radiation-grafted alkaline membranes for alkaline PEM fuel cell applications, as such membranes have certain advantages over other kinds of alkaline membranes, including well-controlled composition, functionality, and other promising properties. To facilitate research and development in this area, the present paper reviews radiation-grafted alkaline membranes. We examine their synthesis/fabrication/characterization, membrane material selection, and theoretical approaches for fundamental understanding. We also present detailed examinations of their application in fuel cell in terms of the working principles of the radiation grafting process, the fabrication of MEAs using radiation-grafted membranes, the membranes' corresponding performance in alkaline PEM fuel cells, as well as performance optimization. The paper also summarizes the challenges and mitigation strategies for radiation-grafted alkaline membranes and their application in PEM fuel cells, presenting an overall picture of the technology as it presently stands.

  19. Radiation-Grafted Polymer Electrolyte Membranes for Water Electrolysis Cells: Evaluation of Key Membrane Properties.

    PubMed

    Albert, Albert; Barnett, Alejandro O; Thomassen, Magnus S; Schmidt, Thomas J; Gubler, Lorenz

    2015-10-14

    Radiation-grafted membranes can be considered an alternative to perfluorosulfonic acid (PFSA) membranes, such as Nafion, in a solid polymer electrolyte electrolyzer. Styrene, acrylonitrile, and 1,3-diisopropenylbenzene monomers are cografted into preirradiated 50 μm ethylene tetrafluoroethylene (ETFE) base film, followed by sulfonation to introduce proton exchange sites to the obtained grafted films. The incorporation of grafts throughout the thickness is demonstrated by scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDX) analysis of the membrane cross-sections. The membranes are analyzed in terms of grafting kinetics, ion-exchange capacity (IEC), and water uptake. The key properties of radiation-grafted membranes and Nafion, such as gas crossover, area resistance, and mechanical properties, are evaluated and compared. The plot of hydrogen crossover versus area resistance of the membranes results in a property map that indicates the target areas for membrane development for electrolyzer applications. Tensile tests are performed to assess the mechanical properties of the membranes. Finally, these three properties are combined to establish a figure of merit, which indicates that radiation-grafted membranes obtained in the present study are promising candidates with properties superior to those of Nafion membranes. A water electrolysis cell test is performed as proof of principle, including a comparison to a commercial membrane electrode assembly (MEA). PMID:26393461

  20. Prism-patterned Nafion membrane for enhanced water transport in polymer electrolyte membrane fuel cell

    NASA Astrophysics Data System (ADS)

    Kim, Sang Moon; Kang, Yun Sik; Ahn, Chiyeong; Jang, Segeun; Kim, Minhyoung; Sung, Yung-Eun; Yoo, Sung Jong; Choi, Mansoo

    2016-06-01

    Here, we report a simple and effective strategy to enhance the performance of the polymer electrolyte membrane fuel cell by imprinting prism-patterned arrays onto the Nafion membrane, which provides three combined effects directly related to the device performance. First, a locally thinned membrane via imprinted micro prism-structures lead to reduced membrane resistance, which is confirmed by electrochemical impedance spectroscopy. Second, increments of the geometrical surface area of the prism-patterned Nafion membrane compared to a flat membrane result in the increase in the electrochemical active surface area. Third, the vertically asymmetric geometry of prism structures in the cathode catalyst layer lead to enhanced water transport, which is confirmed by oxygen gain calculation. To explain the enhanced water transport, we propose a simple theoretical model on removal of water droplets existing in the asymmetric catalyst layer. These three combined effects achieved via incorporating prism patterned arrays into the Nafion membrane effectively enhance the performance of the polymer electrolyte membrane fuel cell.

  1. Pyro-electrification of polymer membranes for cell patterning

    NASA Astrophysics Data System (ADS)

    Rega, R.; Gennari, O.; Mecozzia, L.; Grilli, S.; Pagliarulo, V.; Ferraro, P.

    2016-05-01

    In the recent years, much attention has been devoted to the possibility of charging polymer-based materials, due to their potential in developing large-scale and inexpensive flexible thin-film technology. The availability of localized electrostatic fields is in of great interest for a huge amount of applications such as distribution of biomolecules and cells from the liquid phase. Here we report a voltage-free pyro-electrification (PE) process able to induce permanent dipoles into polymer layers; the lithium niobate (LN) crystal is the key component that plays the multi-purpose role of sustaining, heating and poling the polymer layer that is then peeled-off easily in order to have a free-standing charged membrane. The results show the fascinating application for the living cell patterning. It well known that cell behaviour is affected by chemical and topographical cues of substrate. In fact, polymers, such as polystyrene (PS) and poly(methyl methacrylate) (PMMA), are naturally cytophobic and require specific functionalization treatments in order to promote cell adhesion. Through our proposal technique, it's possible to obtain spontaneous organization and a driven growth of SH-SY5Y cells that is solely dictated by the nature of the charge polymer surface, opening, in this way, the innovative chance to manipulate and transfer biological samples on a free-standing polymer layer [1].

  2. Functionalized polymer nanofibre membranes for protection from chemical warfare stimulants

    NASA Astrophysics Data System (ADS)

    Ramaseshan, Ramakrishnan; Sundarrajan, Subramanian; Liu, Yingjun; Barhate, R. S.; Lala, Neeta L.; Ramakrishna, S.

    2006-06-01

    A catalyst for the detoxification of nerve agents is synthesized from β-cyclodextrin (β-CD) and o-iodosobenzoic acid (IBA). Functionalized polymer nanofibre membranes from PVC polymer are fabricated with β-CD, IBA, a blend of β-CD+IBA, and the synthesized catalyst. These functionalized nanofibres are then tested for the decontamination of paraoxon, a nerve agent stimulant, and it is observed that the stimulant gets hydrolysed. The kinetics of hydrolysis is investigated using UV spectroscopy. The rates of hydrolysis for different organophosphate hydrolyzing agents are compared. The reactivity and amount of adsorption of these catalysts are of higher capacity than the conventionally used activated charcoal. A new design for protective wear is proposed based on the functionalized nanofibre membrane.

  3. Undulatory swimming in fluids with polymer networks

    NASA Astrophysics Data System (ADS)

    Gagnon, D. A.; Shen, X. N.; Arratia, P. E.

    2013-10-01

    The motility behavior of the nematode Caenorhabditis elegans in polymeric solutions of varying concentrations is systematically investigated in experiments using tracking and velocimetry methods. As the polymer concentration is increased, the solution undergoes a transition from the semi-dilute to the concentrated regime, where these rod-like polymers entangle, align, and form networks. Remarkably, we find an enhancement in the nematode's swimming speed of approximately 65% in concentrated solutions compared to semi-dilute solutions. Using velocimetry methods, we show that the undulatory swimming motion of the nematode induces an anisotropic mechanical response in the fluid. This anisotropy, which arises from the fluid micro-structure, is responsible for the observed increase in swimming speed.

  4. Undulatory Swimming in Fluids with Polymer Networks

    NASA Astrophysics Data System (ADS)

    Gagnon, David; Shen, Xiaoning; Arratia, Paulo

    2013-11-01

    In this talk, we systematically investigate the motility behavior of the nematode Caenorhabditis elegans in polymeric solutions of varying concentration using tracking and velocimetry methods. As the polymer concentration is increased, the solution undergoes a transition from the semi-dilute to the concentrated regime, where these rod-like polymers entangle, align, and form networks. Remarkably, we find an enhancement in the nematode's swimming speed of approximately 65 percent in concentrated solutions compared to semi-dilute solutions. Using velocimetry methods, we show that the undulatory swimming motion of the nematode induces an anisotropic mechanical response in the fluid. This anisotropy, which arises from the fluid micro-structure, is responsible for the observed increase in swimming speed. This work was supported by NSF CAREER (CBET) 0954084.

  5. Gradiently crosslinked polymer electrolyte membranes in fuel cells

    NASA Astrophysics Data System (ADS)

    An, De; Wu, Bin; Zhang, Genlei; Zhang, Wen; Wang, Yuxin

    2016-01-01

    Polymer electrolyte membranes in fuel cells should be high in both ionic conductivity and mechanical strength. However, the two are often exclusive to each other. To solve this conundrum, a novel strategy is proposed in this paper, with extensively researched sulfonated poly (ether ether ketone) (SPEEK) membrane as a paradigm. A SPEEK membrane of high sulfonation degree is simply post-treated with NaBH4 and H2SO4 solution at ambient temperature for a certain time to afford the membrane with a gradient crosslinking structure. Measurements via 1H NMR, ATR-FTIR and SEM-EDS are conducted to verify such structural changes. The gradient crosslinks make practically no damage to proton conductance, but effectively restrain the membrane from over swelling and greatly enhance its tensile strength. A H2-O2 fuel cell with the gradiently crosslinked SPEEK membrane shows a maximal power density of 533 mW cm-2 at 80 °C, whereas the fuel cell with the pristine SPEEK membrane cannot be operated beyond 30 °C.

  6. Polymer nanosieve membranes for CO2-capture applications

    NASA Astrophysics Data System (ADS)

    Du, Naiying; Park, Ho Bum; Robertson, Gilles P.; Dal-Cin, Mauro M.; Visser, Tymen; Scoles, Ludmila; Guiver, Michael D.

    2011-05-01

    Microporous organic polymers (MOPs) are of potential significance for gas storage, gas separation and low-dielectric applications. Among many approaches for obtaining such materials, solution-processable MOPs derived from rigid and contorted macromolecular structures are promising because of their excellent mass transport and mass exchange capability. Here we show a class of amorphous MOP, prepared by [2+3] cycloaddition modification of a polymer containing an aromatic nitrile group with an azide compound, showing super-permeable characteristics and outstanding CO2 separation performance, even under polymer plasticization conditions such as CO2/light gas mixtures. This unprecedented result arises from the introduction of tetrazole groups into highly microporous polymeric frameworks, leading to more favourable CO2 sorption with superior affinity in gas mixtures, and selective CO2 transport by presorbed CO2 molecules that limit access by other light gas molecules. This strategy provides a direction in the design of MOP membrane materials for economic CO2 capture processes.

  7. Controlling the localization of polymer-functionalized nanoparticles in mixed lipid/polymer membranes.

    PubMed

    Olubummo, Adekunle; Schulz, Matthias; Lechner, Bob-Dan; Scholtysek, Peggy; Bacia, Kirsten; Blume, Alfred; Kressler, Jörg; Binder, Wolfgang H

    2012-10-23

    Surface hydrophobicity plays a significant role in controlling the interactions between nanoparticles and lipid membranes. In principle, a nanoparticle can be encapsulated into a liposome, either being incorporated into the hydrophobic bilayer interior or trapped within the aqueous vesicle core. In this paper, we demonstrate the preparation and characterization of polymer-functionalized CdSe NPs, tuning their interaction with mixed lipid/polymer membranes from 1,2-dipalmitoyl-sn-glycero-3-phophocholine and PIB(87)-b-PEO(17) block copolymer by varying their surface hydrophobicity. It is observed that hydrophobic PIB-modified CdSe NPs can be selectively located within polymer domains in a mixed lipid/polymer monolayer at the air/water interface, changing their typical domain morphologies, while amphiphilic PIB-PEO-modified CdSe NPs showed no specific localization in phase-separated lipid/polymer films. In addition, hydrophilic water-soluble CdSe NPs can readily adsorb onto spread monolayers, showing a larger effect on the molecule packing at the air/water interface in the case of pure lipid films compared to mixed monolayers. Furthermore, the incorporation of PIB-modified CdSe NPs into hybrid lipid/polymer GUVs is demonstrated with respect to the prevailing phase state of the hybrid membrane. Monitoring fluorescent-labeled PIB-CdSe NPs embedded into phase-separated vesicles, it is demonstrated that they are enriched in one specific phase, thus probing their selective incorporation into the hydrophobic portion of PIB(87)-b-PEO(17) BCP-rich domains. Thus, the formation of biocompatible hybrid GUVs with selectively incorporated nanoparticles opens a new perspective for subtle engineering of membranes together with their (nano-) phase structure serving as a model system in designing functional nanomaterials for effective nanomedicine or drug delivery. PMID:22950802

  8. Mechanisms of gas permeation through polymer membranes. Summary technical report, September 1989--August 1991

    SciTech Connect

    Stern, S.A.

    1991-12-31

    The objective of the present study is to investigate the mechanisms of gas transport in and through polymer membranes and the dependence of these mechanisms on pressure and temperature. This information is required for the development of new, energy-efficient membrane processes for the separation of industrial gas mixtures. Such processes are based on the selective permeation of the components of gas mixtures through nonporous polymer membranes. Recent work has been focused on the permeation of gases through membranes made from glassy polymers, i.e., at temperatures below the glass transition of the polymers (Tg). Glassy polymers are very useful membrane materials for gas separations because of their high selectivity toward different gases. Gases permeate through nonporous polymer membranes by a ``solution-diffusion`` process. Consequently, in order to understand the characteristics of this process it is necessary to investigate also the mechanisms of gas solution and diffusion in glassy polymers. 23 refs., 10 figs., 4 tabs.

  9. Polymer networks and gels: Simulation and theory

    NASA Astrophysics Data System (ADS)

    Kenkare, Nirupama Ramamurthy

    1998-12-01

    The purpose of this research is to understand the molecular origins of the dynamic and swelling properties of polymer networks and gels. Our approach has been to apply computer simulations techniques to off-lattice, near-perfect, trifunctional and tetrafunctional network models. The networks are constructed by endlinking freely-jointed, tangent-hard-sphere chains. Equilibrium discontinuous molecular dynamics techniques are employed to simulate the relaxation of large networks of chain lengths ranging from N = 20 to N = 150 at a packing fraction of 0.43. The simulation trajectories are used to calculate the radius of gyration and end-to-end distance of the network chains, the static structure factor of the crosslinks, the mean-squared displacement of the crosslinks and chain inner segments, the intermediate scattering function of the chains and the elastic modulus of the network. The structure and properties of the networks are shown to depend heavily on the manner in which the network is initially constructed. The dynamics of the network crosslinks and chain inner segments are similar to those of melt chains at short times and show evidence of spatial localization at long times. The results from the elastic moduli and long-time crosslink and chain displacement calculations indicate that entanglement constraints act in conjunction with crosslink constraints to reduce crosslink and chain mobility. The presence of entanglements appears to cause the magnitude of the elastic modulus to be larger than the affine/phantom model predictions. The pressure-volume behavior and the chain configurational properties of deformed networks are investigated over a range of packing fractions. The variation of network pressure with density is found to be similar to that of uncrosslinked chain systems of the same chain length, except at low densities where the network pressures become negative due to elastic effects. We derive a simple, mean-field network equation of state in which the

  10. Tethered and Polymer Supported Bilayer Lipid Membranes: Structure and Function

    PubMed Central

    Andersson, Jakob; Köper, Ingo

    2016-01-01

    Solid supported bilayer lipid membranes are model systems to mimic natural cell membranes in order to understand structural and functional properties of such systems. The use of a model system allows for the use of a wide variety of analytical tools including atomic force microscopy, impedance spectroscopy, neutron reflectometry, and surface plasmon resonance spectroscopy. Among the large number of different types of model membranes polymer-supported and tethered lipid bilayers have been shown to be versatile and useful systems. Both systems consist of a lipid bilayer, which is de-coupled from an underlying support by a spacer cushion. Both systems will be reviewed, with an emphasis on the effect that the spacer moiety has on the bilayer properties. PMID:27249006

  11. Tethered and Polymer Supported Bilayer Lipid Membranes: Structure and Function.

    PubMed

    Andersson, Jakob; Köper, Ingo

    2016-01-01

    Solid supported bilayer lipid membranes are model systems to mimic natural cell membranes in order to understand structural and functional properties of such systems. The use of a model system allows for the use of a wide variety of analytical tools including atomic force microscopy, impedance spectroscopy, neutron reflectometry, and surface plasmon resonance spectroscopy. Among the large number of different types of model membranes polymer-supported and tethered lipid bilayers have been shown to be versatile and useful systems. Both systems consist of a lipid bilayer, which is de-coupled from an underlying support by a spacer cushion. Both systems will be reviewed, with an emphasis on the effect that the spacer moiety has on the bilayer properties. PMID:27249006

  12. Fouling of microfiltration membranes by organic polymer coagulants and flocculants: controlling factors and mechanisms.

    PubMed

    Wang, Sen; Liu, Charles; Li, Qilin

    2011-01-01

    Organic polymers are commonly used as coagulants or flocculants in pretreatment for microfiltration (MF). These high molecular weight compounds are potential membrane foulants when carried over to the MF filters. This study examined fouling of three MF membranes of different materials by three commonly used water treatment polymers: poly(diallyldimethylammonium) chloride (pDADMAC), polyacrylamide (PAM), and poly(acrylic acid-co-acrylamide (PACA) with a wide range of molecular weights. The effects of polymer molecular characteristics, membrane surface properties, solution condition and polymer concentration on membrane fouling were investigated. Results showed severe fouling of microfiltration membranes at very low polymer concentrations, suggesting that residual polymers carried over from the coagulation/flocculation basin can contribute significantly to membrane fouling. The interactions between polymers and membranes depended strongly on the molecular size and charge of the polymer. High molecular weight, positively charged polymers caused the greatest fouling. Blockage of membrane pore openings was identified as the main fouling mechanism with no detectable internal fouling in spite of the small molecular size of the polymers relative to the membrane pore size. Solution conditions (e.g., pH and calcium concentration) that led to larger polymer molecular or aggregate sizes resulted in greater fouling. PMID:20828779

  13. Linked in: immunologic membrane nanotube networks.

    PubMed

    Zaccard, C R; Rinaldo, C R; Mailliard, R B

    2016-07-01

    Membrane nanotubes, also termed tunneling nanotubes, are F-actin-based structures that can form direct cytoplasmic connections and support rapid communication between distant cells. These nanoscale conduits have been observed in diverse cell types, including immune, neuronal, stromal, cancer, and stem cells. Until recently, little was known about the mechanisms involved in membrane nanotube development in myeloid origin APCs or how membrane nanotube networks support their ability to bridge innate and adaptive immunity. New research has provided insight into the modes of induction and regulation of the immune process of "reticulation" or the development of multicellular membrane nanotube networks in dendritic cells. Preprogramming by acute type 1 inflammatory mediators at their immature stage licenses mature type 1-polarized dendritic cells to reticulate upon subsequent interaction with CD40 ligand-expressing CD4(+) Th cells. Dendritic cell reticulation can support direct antigen transfer for amplification of specific T cell responses and can be positively or negatively regulated by signals from distinct Th cell subsets. Membrane nanotubes not only enhance the ability of immature dendritic cells to sense pathogens and rapidly mobilize nearby antigen-presenting cells in the peripheral tissues but also likely support communication of pathogen-related information from mature migratory dendritic cells to resident dendritic cells in lymph nodes. Therefore, the reticulation process facilitates a coordinated multicellular response for the efficient initiation of cell-mediated adaptive immune responses. Herein, we discuss studies focused on the molecular mechanisms of membrane nanotube formation, structure, and function in the context of immunity and how pathogens, such as HIV-1, may use dendritic cell reticulation to circumvent host defenses. PMID:26931578

  14. Better Proton-Conducting Polymers for Fuel-Cell Membranes

    NASA Technical Reports Server (NTRS)

    Narayan, Sri; Reddy, Prakash

    2012-01-01

    Polyoxyphenylene triazole sulfonic acid has been proposed as a basis for development of improved proton-conducting polymeric materials for solid-electrolyte membranes in hydrogen/air fuel cells. Heretofore, the proton-conducting membrane materials of choice have been exemplified by a family of perfluorosulfonic acid-based polymers (Nafion7 or equivalent). These materials are suitable for operation in the temperature of 75 to 85 C, but in order to reduce the sizes and/or increase the energy-conversion efficiencies of fuel-cell systems, it would be desirable to increase temperatures to as high as 120 C for transportation applications, and to as high as 180 C for stationary applications. However, at 120 C and at relative humidity values below 50 percent, the loss of water from perfluorosulfonic acid-based polymer membranes results in fuel-cell power densities too low to be of practical value. Therefore, membrane electrolyte materials that have usefully high proton conductivity in the temperature range of 180 C at low relative humidity and that do not rely on water for proton conduction at 180 C would be desirable. The proposed polyoxyphenylene triazole sulfonic acid-based materials have been conjectured to have these desirable properties. These materials would be free of volatile or mobile acid constituents. The generic molecular structure of these materials is intended to exploit the fact, demonstrated in previous research, that materials that contain ionizable acid and base groups covalently attached to thermally stable polymer backbones exhibit proton conduction even in the anhydrous state.

  15. Development of structured polymer electrolyte membranes for fuel cell applications

    NASA Astrophysics Data System (ADS)

    Gasa, Jeffrey

    The objective of this research was to explore structure-property relationships to develop the understanding needed for introduction of superior PEM materials. Polymer electrolyte membranes based on sulfonated poly(ether ketone ketone) (SPEKK) were fabricated using N-methyl pyrrolidone as casting solvent. The membranes were characterized in terms of properties that were relevant to fuel cell applications, such as proton conductivity, methanol permeability, and swelling properties, among others. It was found in this study that the proton conductivity of neat SPEKK membranes could reach the conductivity of commercial membranes such as NafionRTM. However, when the conductivity of SPEKK was comparable to NafionRTM, the swelling of SPEKK in water was quite excessive. The swelling problem was remedied by modifying the microstructure of SPEKK using different techniques. One of them involved blending of lightly sulfonated PEKK with highly acidic particles (sulfonated crosslinked polystyrene-SXLPS). Low sulfonation level of SPEKK was used to reduce the swelling of the membrane in water and the role of the highly acidic particles was to enhance the proton conductivity of the membrane. Because of the residual crystallinity in SPEKK with low sulfonation levels (IEC < 1 meq/g), the composite membranes exhibited excellent dimensional stability in water at elevated temperatures (30-90 °C). Also, the resistance to swelling of these composite membranes in methanol-water mixtures was far better than NafionRTM, and so was the methanol permeability. Another technique explored was blending with non-conductive polymers (poly(ether imide) and poly(ether sulfone)) to act as mechanical reinforcement. It was found that miscibility behavior of the blends had a significant impact on the transport and swelling properties of these blends, which could be explained by the blend microstructure. The miscibility behavior was found to be strongly dependent on the sulfonation level of SPEKK. The

  16. Conductivity and Stability of Photopolymerized Polymer Electrolyte Network

    NASA Astrophysics Data System (ADS)

    Kyu, Thein; He, Ruixuan; Chen, Yu-Ming; Mao, Jialin; Zhu, Yu; Kyu'S Group, , Dr.; Zhu'S Group Collaboration, , Dr.

    2014-03-01

    A melt-processing window has been identified within the wide isotropic region of the phase diagram of ternary blends consisting of poly (ethylene glycol diacrylate) (PEGDA), tetraethylene glycol dimethyl ether (TEGDME) and lithium bis(trifluoromethane) sulfonamide (LiTFSI). Upon UV-crosslinking of PEGDA in the isotropic window, the polymer electrolyte membrane (PEM) network thus formed is completely transparent and remains in the single phase without undergoing polymerization-induced phase separation or polymerization-induced crystallization. These PEM networks are solid albeit flexible and light-weight with safety and space saving attributes. The ionic conductivity as determined by AC impedance spectroscopy exhibited very high room-temperature ionic conductivity on the order of ~10-3 S/cm in several compositions, viz., 10/45/45, 20/40/40 and 30/35/35 PEGDA/TEGDME/LiTFSI networks. Cyclic voltammetry measurement of these solid-state PEM networks revealed excellent electrochemical stability against lithium reference electrode. The above study has been extended to the anode (graphite) and cathode (LiFePO4) half-cell configurations with lithium as counter electrode. Charge/discharge cycling behavior of these half cells will be discussed. Supported by NSF-DMR 1161070 and University of Akron.

  17. Dynamic assembly of polymer nanotube networks via kinesin powered microtubule filaments

    SciTech Connect

    Paxton, Walter F.; Bachand, George D.; Gomez, Andrew; Henderson, Ian M.; Bouxsein, Nathan F.

    2015-04-24

    In this study, we describe for the first time how biological nanomotors may be used to actively self-assemble mesoscale networks composed of diblock copolymer nanotubes. The collective force generated by multiple kinesin nanomotors acting on a microtubule filament is large enough to overcome the energy barrier required to extract nanotubes from polymer vesicles comprised of poly(ethylene oxide-b-butadiene) in spite of the higher force requirements relative to extracting nanotubes from lipid vesicles. Nevertheless, large-scale polymer networks were dynamically assembled by the motors. These networks displayed enhanced robustness, persisting more than 24 h post-assembly (compared to 4–5 h for corresponding lipid networks). The transport of materials in and on the polymer membranes differs substantially from the transport on analogous lipid networks. Specifically, our data suggest that polymer mobility in nanotubular structures is considerably different from planar or 3D structures, and is stunted by 1D confinement of the polymer subunits. Moreover, quantum dots adsorbed onto polymer nanotubes are completely immobile, which is related to this 1D confinement effect and is in stark contrast to the highly fluid transport observed on lipid tubules.

  18. Dynamic assembly of polymer nanotube networks via kinesin powered microtubule filaments

    DOE PAGESBeta

    Paxton, Walter F.; Bachand, George D.; Gomez, Andrew; Henderson, Ian M.; Bouxsein, Nathan F.

    2015-04-24

    In this study, we describe for the first time how biological nanomotors may be used to actively self-assemble mesoscale networks composed of diblock copolymer nanotubes. The collective force generated by multiple kinesin nanomotors acting on a microtubule filament is large enough to overcome the energy barrier required to extract nanotubes from polymer vesicles comprised of poly(ethylene oxide-b-butadiene) in spite of the higher force requirements relative to extracting nanotubes from lipid vesicles. Nevertheless, large-scale polymer networks were dynamically assembled by the motors. These networks displayed enhanced robustness, persisting more than 24 h post-assembly (compared to 4–5 h for corresponding lipid networks).more » The transport of materials in and on the polymer membranes differs substantially from the transport on analogous lipid networks. Specifically, our data suggest that polymer mobility in nanotubular structures is considerably different from planar or 3D structures, and is stunted by 1D confinement of the polymer subunits. Moreover, quantum dots adsorbed onto polymer nanotubes are completely immobile, which is related to this 1D confinement effect and is in stark contrast to the highly fluid transport observed on lipid tubules.« less

  19. Developments of Novel Polymer Electrolyte Fuel Cell Membranes

    NASA Astrophysics Data System (ADS)

    Irita, Tomomi; Kondo, Masahiro; Aoyama, Hirokazu; Russell, Thomas

    2006-03-01

    Perfluorinated polymer electrolyte membranes (PEM), such as Nafion, are considered to be the most promising candidate for the development of the next generation fuel cell technology. The key technological challenges facing PEMs are their performance, durability and cost. In this research, the polymer electrolyte emulsions (PEE) were obtained by a simple hydrolysis reaction of the precursor polymer emulsion. PEMs are obtained by solvent casting the PEE. The PEE obtained here has a very low viscosity even at high solution concentrations. Using high concentration emulsions greatly reduces the amount of the waste, which makes this technology superior to the conventional ones. Casting conditions were optimized to enhance the mechanical properties, e.g. the tensile strength and viscoelastic properties, of the membrane. The PEMs obtained possessed better ionic conductivity than Nafion while their mechanical properties are comparable. Finally, the cost evaluation for this process was conducted and it was shown that the contribution to the cost reduction becomes bigger. (This research was sponsored by New Energy and Industrial Technology Development Organization, Japan)

  20. Positron annihilation in cardo-based polymer membranes.

    PubMed

    Kobayashi, Y; Kazama, Shingo; Inoue, K; Toyama, T; Nagai, Y; Haraya, K; Mohamed, Hamdy F M; O'Rouke, B E; Oshima, N; Kinomura, A; Suzuki, R

    2014-06-01

    Positron annihilation lifetime spectroscopy (PALS) is applied to a series of bis(aniline)fluorene and bis(xylidine)fluorene-based cardo polyimide and bis(phenol)fluorene-based polysulfone membranes. It was found that favorable amounts of positronium (Ps, the positron-electron bound state) form in cardo polyimides with the 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) moiety and bis(phenol)fluorene-based cardo polysulfone, but no Ps forms in most of the polyimides with pyromellitic dianhydride (PMDA) and 3,3',4,4'-biphenyltetracarboxylic dianhydride (BTDA) moieties. A bis(xylidine)fluorene-based polyimide membrane containing PMDA and BTDA moieties exhibits a little Ps formation but the ortho-positronium (o-Ps, the triplet state of Ps) lifetime of this membrane anomalously shortens with increasing temperature, which we attribute to chemical reaction of o-Ps. Correlation between the hole size (V(h)) deduced from the o-Ps lifetime and diffusion coefficients of O2 and N2 for polyimides with the 6FDA moiety and cardo polysulfone showing favorable Ps formation is discussed based on free volume theory of gas diffusion. It is suggested that o-Ps has a strong tendency to probe larger holes in rigid chain polymers with wide hole size distributions such as those containing cardo moieties, resulting in deviations from the previously reported correlations for common polymers such as polystyrene, polycarbonate, polysulfone, and so forth. PMID:24815092

  1. New molecularly-imprinted polymer for carnitine and its application as ionophore in potentiometric selective membranes.

    PubMed

    Moret, Joséphine; Moreira, Felismina T C; Almeida, Sofia A A; Sales, M Goreti F

    2014-10-01

    Carnitine (CRT) is a biological metabolite found in urine that contributes in assessingseveral disease conditions, including cancer. Novel quick screening procedures for CRT are therefore fundamental. This work proposes a novel potentiometric device where molecularly imprinted polymers (MIPs) were used as ionophores. The host-tailored sites were imprinted on a polymeric network assembled by radical polymerization of methacrylic acid (MAA) and trimethylpropane trimethacrylate (TRIM). Non-imprinted polymers (NIPs) were produced as control by removing the template from the reaction media. The selective membrane was prepared by dispersing MIP or NIP particles in plasticizer and poly(vinyl chloride), PVC, and casting this mixture over a solid contact support made of graphite. The composition of the selective membrane was investigated with regard to kind/amount of sensory material (MIP or NIP), and the need for a lipophilic additive. Overall, MIP sensors with additive exhibited the best performance, with near-Nernstian response down to ~1×10(-4)mol L(-1), at pH5, and a detection limit of ~8×10(-5)mol L(-1). Suitable selectivity was found for all membranes, assessed by the matched potential method against some of the most common species in urine (urea, sodium, creatinine, sulfate, fructose and hemoglobin). CRT selective membranes including MIP materials were applied successfully to the potentiometric determination of CRT in urine samples. PMID:25175239

  2. Covalently crosslinked diels-alder polymer networks.

    SciTech Connect

    Bowman, Christopher; Adzima, Brian J.; Anderson, Benjamin John

    2011-09-01

    This project examines the utility of cycloaddition reactions for the synthesis of polymer networks. Cycloaddition reactions are desirable because they produce no unwanted side reactions or small molecules, allowing for the formation of high molecular weight species and glassy crosslinked networks. Both the Diels-Alder reaction and the copper-catalyzed azide-alkyne cycloaddition (CuAAC) were studied. Accomplishments include externally triggered healing of a thermoreversible covalent network via self-limited hysteresis heating, the creation of Diels-Alder based photoresists, and the successful photochemical catalysis of CuAAC as an alternative to the use of ascorbic acid for the generation of Cu(I) in click reactions. An analysis of the results reveals that these new methods offer the promise of efficiently creating robust, high molecular weight species and delicate three dimensional structures that incorporate chemical functionality in the patterned material. This work was performed under a Strategic Partnerships LDRD during FY10 and FY11 as part of a Sandia National Laboratories/University of Colorado-Boulder Excellence in Science and Engineering Fellowship awarded to Brian J. Adzima, a graduate student at UC-Boulder. Benjamin J. Anderson (Org. 1833) was the Sandia National Laboratories point-of-contact for this fellowship.

  3. Monte Carlo studies of interpenetrating polymer network formation

    NASA Astrophysics Data System (ADS)

    Schulz, Michael; Frisch, Harry L.

    1994-12-01

    We present a lattice Monte-Carlo simulation of polymer network formation using the bond fluctuation method. We apply this procedure to simulate the formation of a class of simultaneous interpenetrating polymer networks (IPNs) which has been experimentally studied consisting of one network crosslinked with a trifunctional monomer (PCU) and another crosslinked with a tetrafunctional monomer (the free radical vinyl polymer network). The numerical simulation reveals essentially all features found experimentally for this class of IPNs. The system composition and initial morphology, at least for reactions which are relatively fast compared to the uphill diffusion process causing phase separation, is in good agreement with a mean field [random-phase approximations (RPA)] theory.

  4. Viscoelasticity of reversibly crosslinked networks of semiflexible polymers

    NASA Astrophysics Data System (ADS)

    Plagge, Jan; Fischer, Andreas; Heussinger, Claus

    2016-06-01

    We present a theoretical framework for the linear and nonlinear viscoelastic properties of reversibly crosslinked networks of semiflexible polymers. In contrast to affine models where network strain couples to the polymer end-to-end distance, in our model strain rather serves to locally distort the network structure. This induces bending modes in the polymer filaments, the properties of which are slaved to the surrounding network structure. Specifically, we investigate the frequency-dependent linear rheology, in particular in combination with crosslink binding-unbinding processes. We also develop schematic extensions to describe the nonlinear response during creep measurements as well as during constant strain-rate ramps.

  5. Free-standing membrane polymer laser on the end of an optical fiber

    NASA Astrophysics Data System (ADS)

    Zhai, Tianrui; Chen, Li; Li, Songtao; Hu, Yujie; Wang, Yimeng; Wang, Li; Zhang, Xinping

    2016-01-01

    One- and two-dimensional distributed feedback cavities were constructed on free-standing polymer membranes using spin-coating and lift-off techniques. Low threshold lasing was generated through feedback amplification when the 290-nm membrane device was optically pumped, which was attributed to the strong confinement mechanism provided by the active waveguide layer without a substrate. The free-standing membrane polymer laser is flexible and can be transplanted. Single- and dual-wavelength fiber lasers were achieved by directly attaching the membrane polymer laser on the optical fiber end face. This technique provides potential to fabricate polymer lasers on surfaces with arbitrary shapes.

  6. Study of transport through an electro responsive polymer membrane

    NASA Astrophysics Data System (ADS)

    Das, D.; Datta, A.; Contractor, A. Q.

    2015-02-01

    Conducting polymers have been used widely for development of several electronic, sensing devices because of its electro active nature. In the present work porous polycarbonate (PC) support was coated with a thin gold layer. An electrochemically synthesized polyaniline (PANI) film was deposited on gold coated PC and characterisation was done by field emission gun scanning electron microscopy (FEG-SEM), transmission electron microscopy (TEM) and atomic force microscopy (AFM). For measuring the concentration of potassium ion (K+) inductively coupled plasma atomic emission spectrometry (ICP-AES) was used. Potassium ion transport across PANI membrane at various potential showed the gradual opening of the coiled PANI. In this work an effort has been given to picture the situation in the membrane electrolyte junction on application of potential.

  7. Interpenetrating polymer networks from acetylene terminated materials

    NASA Technical Reports Server (NTRS)

    Connell, J. W.; Hergenrother, P. M.

    1989-01-01

    As part of a program to develop high temperature/high performance structural resins for aerospace applications, the chemistry and properties of a novel class of interpenetrating polymer networks (IPNs) were investigated. These IPNs consist of a simple diacetylenic compound (aspartimide) blended with an acetylene terminated arylene ether oligomer. Various compositional blends were prepared and thermally cured to evaluate the effect of crosslink density on resin properties. The cured IPNs exhibited glass transition temperatures ranging from 197 to 254 C depending upon the composition and cure temperature. The solvent resistance, fracture toughness and coefficient of thermal expansion of the cured blends were related to the crosslink density. Isothermal aging of neat resin moldings, adhesive and composite specimens showed a postcure effect which resulted in improved elevated temperature properties. The chemistry, physical and mechanical properties of these materials will be discussed.

  8. A NOVEL HYDROPHILIC POLYMER MEMBRANE FOR THE DEHYDRATION OF ORGANIC SOLVENTS

    EPA Science Inventory

    Novel hydrophilic polymer membranes based on polyallylamine ydrochloride- polyvinylalcohol are developed. The high selectivity and flux characteristics of these membranes for the dehydration of organic solvents are evaluated using pervaporation technology and are found to be ver...

  9. Controlled thermal oxidative crosslinking of polymers of intrinsic microporosity towards tunable molecular sieve membranes

    NASA Astrophysics Data System (ADS)

    Song, Qilei; Cao, Shuai; Pritchard, Robyn H.; Ghalei, Behnam; Al-Muhtaseb, Shaheen A.; Terentjev, Eugene M.; Cheetham, Anthony K.; Sivaniah, Easan

    2014-09-01

    Organic open frameworks with well-defined micropore (pore dimensions below 2 nm) structure are attractive next-generation materials for gas sorption, storage, catalysis and molecular level separations. Polymers of intrinsic microporosity (PIMs) represent a paradigm shift in conceptualizing molecular sieves from conventional ordered frameworks to disordered frameworks with heterogeneous distributions of microporosity. PIMs contain interconnected regions of micropores with high gas permeability but with a level of heterogeneity that compromises their molecular selectivity. Here we report controllable thermal oxidative crosslinking of PIMs by heat treatment in the presence of trace amounts of oxygen. The resulting covalently crosslinked networks are thermally and chemically stable, mechanically flexible and have remarkable selectivity at permeability that is three orders of magnitude higher than commercial polymeric membranes. This study demonstrates that controlled thermochemical reactions can delicately tune the topological structure of channels and pores within microporous polymers and their molecular sieving properties.

  10. Understanding the transport processes in polymer electrolyte membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Cheah, May Jean

    Polymer electrolyte membrane (PEM) fuel cells are energy conversion devices suitable for automotive, stationary and portable applications. An engineering challenge that is hindering the widespread use of PEM fuel cells is the water management issue, where either a lack of water (resulting in membrane dehydration) or an excess accumulation of liquid water (resulting in fuel cell flooding) critically reduces the PEM fuel cell performance. The water management issue is addressed by this dissertation through the study of three transport processes occurring in PEM fuel cells. Water transport within the membrane is a combination of water diffusion down the water activity gradient and the dragging of water molecules by protons when there is a proton current, in a phenomenon termed electro-osmotic drag, EOD. The impact of water diffusion and EOD on the water flux across the membrane is reduced due to water transport resistance at the vapor/membrane interface. The redistribution of water inside the membrane by EOD causes an overall increase in the membrane resistance that regulates the current and thus EOD, thereby preventing membrane dehydration. Liquid water transport in the PEM fuel cell flow channel was examined at different gas flow regimes. At low gas Reynolds numbers, drops transitioned into slugs that are subsequently pushed out of the flow channel by the gas flow. The slug volume is dependent on the geometric shape, the surface wettability and the orientation (with respect to gravity) of the flow channel. The differential pressure required for slug motion primarily depends on the interfacial forces acting along the contact lines at the front and the back of the slug. At high gas Reynolds number, water is removed as a film or as drops depending on the flow channel surface wettability. The shape of growing drops at low and high Reynolds number can be described by a simple interfacial energy minimization model. Under flooding conditions, the fuel cell local current

  11. Poly(vinyl alcohol)/poly(vinyl chloride) composite polymer membranes for secondary zinc electrodes

    NASA Astrophysics Data System (ADS)

    Yang, Chun-Chen; Yang, Jen Ming; Wu, Cheng-Yeou

    A microporous composite polymer membrane composed of poly(vinyl alcohol) (PVA) and poly(vinyl chloride) (PVC), was prepared by a solution casting method and a partial dissolution process. The characteristic properties of microporous PVA/PVC composite polymer membranes containing 2.5-10 wt.% PVC polymers as fillers were characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM), capillary flow porometry (CFP), micro-Raman spectroscopy, dynamic mechanical analyzer (DMA) and the AC impedance method. The electrochemical properties of a secondary Zn electrode with the PVA/PVC composite polymer membrane were studied using the galvanostatic charge/discharge method. The PVA/PVC composite polymer membrane showed good thermal, mechanical and electrochemical properties. As a result, the PVA/PVC composite polymer membrane appears to be a good candidate for use on the secondary Zn electrodes.

  12. High temperature polymers for proton exchange membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Einsla, Brian Russel

    Novel proton exchange membranes (PEMs) were investigated that show potential for operating at higher temperatures in both direct methanol (DMFC) and H 2/air PEM fuel cells. The need for thermally stable polymers immediately suggests the possibility of heterocyclic polymers bearing appropriate ion conducting sites. Accordingly, monomers and random disulfonated poly(arylene ether) copolymers containing either naphthalimide, benzoxazole or benzimidazole moieties were synthesized via direct copolymerization. The ion exchange capacity (IEC) was varied by simply changing the ratio of disulfonated monomer to nonsulfonated monomer in the copolymerization step. Water uptake and proton conductivity of cast membranes increased with IEC. The water uptake of these heterocyclic copolymers was lower than that of comparable disulfonated poly(arylene ether) systems, which is a desirable improvement for PEMs. Membrane electrode assemblies were prepared and the initial fuel cell performance of the disulfonated polyimide and polybenzoxazole (PBO) copolymers was very promising at 80°C compared to the state-of-the-art PEM (NafionRTM); nevertheless these membranes became brittle under operating conditions. Several series of poly(arylene ether)s based on disodium-3,3'-disulfonate-4,4 '-dichlorodiphenylsulfone (S-DCDPS) and a benzimidazole-containing bisphenol were synthesized and afforded copolymers with enhanced stability. Selected properties of these membranes were compared to separately prepared miscible blends of disulfonated poly(arylene ether sulfone) copolymers and polybenzimidazole (PBI). Complexation of the sulfonic acid groups with the PBI structure reduced water swelling and proton conductivity. The enhanced proton conductivity of NafionRTM membranes has been proposed to be due to the aggregation of the highly acidic side-chain sulfonic acid sites to form ion channels. A series of side-chain sulfonated poly(arylene ether sulfone) copolymers based on methoxyhydroquinone was

  13. Wavelength selective polymer network formation of end-functional star polymers.

    PubMed

    Kaupp, Michael; Hiltebrandt, Kai; Trouillet, Vanessa; Mueller, Patrick; Quick, Alexander S; Wegener, Martin; Barner-Kowollik, Christopher

    2016-01-31

    A wavelength selective technique for light-induced network formation based on two photo-active moieties, namely ortho-methylbenzaldehyde and tetrazole is introduced. The network forming species are photo-reactive star polymers generated via reversible activation fragmentation chain transfer (RAFT) polymerization, allowing the network to be based on almost any vinylic monomer. Direct laser writing (DLW) allows to form any complex three-dimensional structure based on the photo-reactive star polymers. PMID:26687371

  14. Proton conducting, composite sulfonated polymer membrane for medium temperature and low relative humidity fuel cells

    NASA Astrophysics Data System (ADS)

    Shin, Dong Won; Kang, Na Rae; Lee, Kang Hyuck; Cho, Doo Hee; Kim, Ji Hoon; Lee, Won Hyo; Lee, Young Moo

    2014-09-01

    Inorganic-organic composite membranes are fabricated using zirconium acetylacetonate nanoparticles and biphenol-based sulfonated poly(arylene ether sulfone) as an inorganic, proton conducting nanomaterial and a polymer matrix, respectively. An amphiphilic surfactant (Pluronic®) induces distribution of the inorganic nanoparticles over the entire polymer membrane. The composite membranes are thermally stable up to 200 °C. Zirconium acetylacetonate improves inter-chain interactions and the robustness of polymer membranes resulting in excellent membrane mechanical properties. In addition, composite membranes show outstanding proton conductivity compared to that of the pristine membrane at medium temperatures (80-120 °C) and low relative humidity (<50%) conditions. This improvement is due to the presence of acetylacetonate anions, which bind water molecules and act as an additional proton conducting site and/or medium. Therefore, the composite membranes significantly outperform the pristine membrane in fuel cell performance tests at medium temperatures and low relative humidity.

  15. Stable trifluorostyrene containing compounds grafted to base polymers, and their use as polymer electrolyte membranes

    DOEpatents

    Yang, Zhen-Yu; Roelofs, Mark Gerrit

    2010-11-09

    A fluorinated ion exchange polymer prepared by grafting at least one grafting monomer on to at least one base polymer, wherein the grafting monomer comprises structure 1a or 1b: wherein Z comprises S, SO.sub.2, or POR wherein R comprises a linear or branched perfluoroalkyl group of 1 to 14 carbon atoms optionally containing oxygen or chlorine, an alkyl group of 1 to 8 carbon atoms, an aryl group of 6 to 12 carbon atoms or a substituted aryl group of 6 to 12 carbon atoms; RF comprises a linear or branched perfluoroalkene group of 1 to 20 carbon atoms, optionally containing oxygen or chlorine; Q is chosen from F, --OM, NH.sub.2, --N(M)SO.sub.2R.sup.2.sub.F, and C(M)(SO.sub.2R.sup.2.sub.F).sub.2, wherein M comprises H, an alkali cation, or ammonium; R.sup.2.sub.F groups comprises alkyl of 1 to 14 carbon atoms which may optionally include ether oxygens or aryl of 6 to 12 carbon atoms where the alkyl or aryl groups may be perfluorinated or partially fluorinated; and n is 1 or 2 for 1a, and n is 1, 2, or 3 for 1b. These ion exchange polymers are useful in preparing catalyst coated membranes and membrane electrode assemblies used in fuel cells.

  16. Membrane electrode assemblies for unitised regenerative polymer electrolyte fuel cells

    NASA Astrophysics Data System (ADS)

    Wittstadt, U.; Wagner, E.; Jungmann, T.

    Membrane electrode assemblies for regenerative polymer electrolyte fuel cells were made by hot pressing and sputtering. The different MEAs are examined in fuel cell and water electrolysis mode at different pressure and temperature conditions. Polarisation curves and ac impedance spectra are used to investigate the influence of the changes in coating technique. The hydrogen gas permeation through the membrane is determined by analysing the produced oxygen in electrolysis mode. The analysis shows, that better performances in both process directions can be achieved with an additional layer of sputtered platinum on the oxygen electrode. Thus, the electrochemical round-trip efficiency can be improved by more than 4%. Treating the oxygen electrode with PTFE solution shows better performance in fuel cell and less performance in electrolysis mode. The increase of the round-trip efficiency is negligible. A layer sputtered directly on the membrane shows good impermeability, and hence results in high voltages at low current densities. The mass transportation is apparently constricted. The gas diffusion layer on the oxygen electrode, in this case a titanium foam, leads to flooding of the cell in fuel cell mode. Stable operation is achieved after pretreatment of the GDL with a PTFE solution.

  17. Porous polymer networks and ion-exchange media and metal-polymer composites made therefrom

    DOEpatents

    Kanatzidis, Mercouri G; Katsoulidis, Alexandros

    2015-03-10

    Porous polymeric networks and composite materials comprising metal nanoparticles distributed in the polymeric networks are provided. Also provided are methods for using the polymeric networks and the composite materials in liquid- and vapor-phase waste remediation applications. The porous polymeric networks, are highly porous, three-dimensional structures characterized by high surface areas. The polymeric networks comprise polymers polymerized from aldehydes and phenolic molecules.

  18. Nano mineral fiber enhanced catalyst coated membranes for improving polymer electrolyte membrane fuel cell durability

    NASA Astrophysics Data System (ADS)

    Xu, Feng; Xu, Ran; Mu, Shichun

    In order to protect the perfluorosulfonic acid (PFSA) ionomer from an attack of contaminant metal ions as well as to enhance the mechanical stability of catalyst layers, palygorskite (PGS) is introduced into the catalyst layer of polymer electrolyte membrane fuel cells. PGS is a widely used natural nano-sized silicate mineral fiber with unique nano-sized channel structure, has a strong absorption capacity for heavy metal ions. We identify a negative influence of Fe 2+ on PFSA membranes to make a comparative study. Subsequently catalyst coated membranes (CCMs) prepared with a PGS-Pt/C composite catalyst show a great effect in reducing Fe 2+ ion crossover. Results display that PGS absorbs Fe 2+ in nano-structure channels, and effectively protect PFSA ionomer in both the catalyst layer and membrane from hydroxyl radicals (OH rad) attack. Thus, the chemical stability of PFSA ionomer in both the catalyst layer and membrane is greatly improved. Furthermore, the enhancement of the mechanical performance of catalyst layers is discussed.

  19. Mechanical and water sorption properties of nafion and composite nafion/titanium dioxide membranes for polymer electrolyte membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Satterfield, May Barclay

    The mechanical properties of the membranes used in polymer electrolyte membrane fuel cells are important to the performance and longevity of the cell. The speed and extent of membrane water uptake depend on the membrane's viscoelastic mechanical properties, which are themselves dependent on membrane hydration, and increased hydration improves membrane proton conductivity and fuel cell performance. Membrane mechanical properties also affect durability and cell longevity, preventing membrane failure from stresses induced by changing temperature and water content during operational cycling. Further, membrane creep and stress-relaxation can change the extent of membrane/electrode contact, also changing cell behavior. New composite membrane materials have exhibited superior performance in fuel cells, and it is suspected that improved mechanical properties are responsible. Studies of polymer electrolyte membrane (PEM) fuel cell dynamics using Nafion membranes have demonstrated the importance of membrane mechanical properties, swelling and water-absorption behavior to cell performance. Nonlinear and delayed dynamic responses to changing operating parameters were unexpected, but reminiscent of polymer viscoelastic behavior and water sorption dynamics, illustrating the need to better understand membrane properties to design and operate fuel cells. Further, Nafion/TiO2 composite membranes developed by the Princeton Chemistry Department improve fuel cell performance, which may be due to changes in membrane microstructure and enhanced mechanical properties. Mechanical properties, stress-relaxation behavior, water sorption and desorption rates and pressures exerted during hydration by a confined membrane have been measured for Nafion and for Nafion/TiO2 composite membranes. Mechanical properties, including the Young's modulus and limits of elastic deformation are dependent on temperature and membrane water content. The Young's modulus decreases with increasing water content and

  20. A review of polymer electrolyte membrane fuel cell stack testing

    NASA Astrophysics Data System (ADS)

    Miller, M.; Bazylak, A.

    This paper presents an overview of polymer electrolyte membrane fuel cell (PEMFC) stack testing. Stack testing is critical for evaluating and demonstrating the viability and durability required for commercial applications. Single cell performance cannot be employed alone to fully derive the expected performance of PEMFC stacks, due to the non-uniformity in potential, temperature, and reactant and product flow distributions observed in stacks. In this paper, we provide a comprehensive review of the state-of-the art in PEMFC testing. We discuss the main topics of investigation, including single cell vs. stack-level performance, cell voltage uniformity, influence of operating conditions, durability and degradation, dynamic operation, and stack demonstrations. We also present opportunities for future work, including the need to verify the impact of stack size and cell voltage uniformity on performance, determine operating conditions for achieving a balance between electrical efficiency and flooding/dry-out, meet lifetime requirements through endurance testing, and develop a stronger understanding of degradation.

  1. Enzyme stabilization by linear chain polymers in ultrafiltration membrane reactors

    SciTech Connect

    Greco, G.; Gianfreda, L.

    1981-10-01

    The experimental results discussed in this article concern pi-nitrophenylphosphate hydrolysis by acid phosphatase in an ultrafiltration membrane reactor. The basic conclusions drawn are : 1) Linking the enzyme to a soluble support does not give rise to an increase in its stability while the chemical manipulations involved result in marked reductions in enzymic activity. 2) Enzyme entrapment within a proteic gel produces a considerable increase in its thermal stability as compared to the diluted native enzyme; this presumably stems from drastic reductions in enzyme mobility. 3) Correspondingly, considerable reductions occur in enzyme activity that depend on substrate mass transfer resistances within the gel layer. 4) Small amounts of linear chain water-soluble synthetic polymers (polyacrylamides) give rise to high macromolecular concentration levels in the reactor region where the enzyme is dynamically immobilized and produce the same enzyme stabilization as gel entrapment. 5) Only minor substrate mass transfer limitations take place in this region and hence enzyme activity is virtually unaffected. 6) Both effects (stabilization and slight activity reduction) seem not to depend strongly on the characteristics of the soluble polymer (molecular weight and ionic character). (Refs. 16).

  2. Phase diagram of hopping conduction mechanisms in polymer nanofiber network

    SciTech Connect

    Li, Jeng-Ting; Lu, Yu-Cheng; Jiang, Shiau-Bin; Zhong, Yuan-Liang; Yeh, Jui-Ming

    2015-12-07

    Network formation by nanofiber crosslinking is usually in polymer materials as application in organic semiconductor devices. Electron hopping transport mechanisms depend on polymer morphology in network. Conducting polymers morphology in a random network structure is modeled by a quasi-one-dimensional system coupled of chains or fibers. We observe the varying hopping conduction mechanisms in the polyaniline nanofibers of the random network structure. The average diameter d of the nanofibers is varied from approximately 10 to 100 nm. The different dominant hopping mechanisms including Efros-Shklovskii variable-range hopping (VRH), Mott VRH, and nearest-neighbor hopping are dependent on temperature range and d in crossover changes. The result of this study is first presented in a phase diagram of hopping conduction mechanisms based on the theories of the random network model. The hopping conduction mechanism is unlike in normal semiconductor materials.

  3. Polymer-Fullerene Network Formation via Light-Induced Crosslinking.

    PubMed

    Sugawara, Yuuki; Hiltebrandt, Kai; Blasco, Eva; Barner-Kowollik, Christopher

    2016-09-01

    A facile and efficient methodology for the formation of polymer-fullerene networks via a light-induced reaction is reported. The photochemical crosslinking is based on a nitrile imine-mediated tetrazole-ene cycloaddition reaction, which proceeds catalyst-free under UV-light irradiation (λmax = 320 nm) at ambient temperature. A tetrazole-functionalized polymer (Mn = 6500 g mol(-1) , Ð = 1.3) and fullerene C60 are employed for the formation of the hybrid networks. The tetrazole-functionalized polymer as well as the fullerene-containing networks are carefully characterized by NMR spectrometry, size exclusion chromatography, infrared spectroscopy, and elemental analysis. Furthermore, thermal analysis of the fullerene networks and their precursors is carried out. The current contribution thus induces an efficient platform technology for fullerene-based network formation. PMID:27336692

  4. Synthesis and characterization of polymer electrolyte membranes with controlled ion transport properties

    NASA Astrophysics Data System (ADS)

    Xu, Kui

    2011-12-01

    Ion-containing block copolymers hold promise as next-generation polymer electrolyte membrane (PEM) materials due to their capability to self-assemble into ordered nanostructures facilitating proton transport over a wide range of conditions. Ion-containing block copolymers, sulfonated poly(styrene- b-vinylidene fluoride-b-styrene), with varied degrees of sulfonation were synthesized. The synthetic strategy involved a new approach to chain-end functionalized poly(vinylidene fluoride) as a macro-initiator followed by atom transfer polymerization of styrene and sulfonation. Characterization of the polymers were extensively carried out by 1H and 19F nuclear magnetic resonance and Fouriertransform infrared spectroscopy, differential scanning calorimetry, and thermogravimetry analysis. Tapping mode atomic force microscopy and transmission electron microscopy were applied to study the phase separation and self-assembled morphology. Strong dependence of ion exchange capacity, water absorption, morphology and proton conductivity on the degree of sulfonation has been found. It has been observed that the conductivities of the block copolymers are considerably higher than the random copolymers of polystyrene and sulfonated polystyrene possessing similar ion exchange capacities. Copolymers of vinylidene fluoride and perfluoro(4-methyl-3,6-dioxane-7-ene) sulfonyl fluoride containing amino end-groups were synthesized for the first time. The prepared aminoterminated polymers underwent cross-linking reactions with 1,3,5-benzene triisocyanate to form proton conductive networks. The chain-end crosslinked fluoropolymer membranes exhibited excellent thermal, hydrolytic and oxidative stabilities. The ion exchange capacity, water uptake, the state of absorbed water, and transport properties of the membranes were found to be highly dependent upon the chemical composition of the copolymers. The cross-linked membranes showed extremely low methanol permeability, while maintaining high proton

  5. Porous networks derived from synthetic polymer-clay complexes

    SciTech Connect

    Carrado, K.A.; Thiyagarajan, P.; Elder, D.L.

    1995-05-12

    Synthetic hectorites were hydrothermally crystallized with direct incorporation of a cationic polymer poly(dimethyl diallyl ammonium chloride) (PDDA), and two neutral cellulosic polymers hydroxypropyl methylcellulose (HPMC) and hydroxyethyl cellulose (HEC). Synthetic PDDA-hectorite displays the lowest d-spacing at 15.8 {Angstrom} along with less polymer incorporation (7.8 wt % organic) than the neutral polymers (18--22 wt % organic). Thermal analysis and small angle neutron scattering were used to further examine the polymer-clay systems. Clay platelets of the largest size and best stacking order occur when cationic PDDA polymer is used. PDDA also enhances these properties over the crystallites prepared for a control mineral, where no polymer is used. HEC acts to aggregate the silica, leaving less to react to form clay. The clay platelets which result from HEC are small, not stacked to a large degree, and oriented randomly. Neutral HPMC acts more like cationic PDDA in that larger clay platelets are allowed to form. The extended microstructure of the clay network remains undisturbed after polymer is removed by calcination. When no polymer is used, the synthetic hectorite has a N{sub 2} BET surface area of 200 M{sup 2}/gm, even after calcination. This increases by 20--50% for the synthetic polymer-hectorites after the polymer is removed by calcination.

  6. Chemical degradation of fluorosulfonamide fuel cell membrane polymer model compounds

    NASA Astrophysics Data System (ADS)

    Alsheheri, Jamela M.; Ghassemi, Hossein; Schiraldi, David A.

    2014-12-01

    The durability of a polymer electrolyte fuel cell membrane, along with high proton conductivity and mechanical performance is critical to the success of these energy conversion devices. Extending our work in perfluorinated membrane stability, aromatic trifluoromethyl sulfonamide model compounds were prepared, and their oxidative degradation was examined. The chemical structures for the models were based on mono-, di- and tri-perfluorinated sulfonamide modified phenyl rings. Durability of the model compounds was evaluated by exposure to hydroxyl radicals generated using Fenton reagent and UV irradiation of hydrogen peroxide. LC-MS results for the mono-substituted model compound indicate greater stability to radical oxidation than the di-substituted species; loss of perfluorinated fonamide side chains appears to be an important pathway, along with dimerization and aromatic ring hydroxylation. The tri-substituted model compound also shows loss of side chains, with the mono-substituted compound being a major oxidation product, along with a limited amount of hydroxylation and dimerization of the starting material.

  7. Polymer-Induced Swelling of Solid-Supported Lipid Membranes

    PubMed Central

    Kreuzer, Martin; Trapp, Marcus; Dahint, Reiner; Steitz, Roland

    2015-01-01

    In this paper, we study the interaction of charged polymers with solid-supported 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) membranes by in-situ neutron reflectivity. We observe an enormous swelling of the oligolamellar lipid bilayer stacks after incubation in solutions of poly(allylamine hydrochloride) (PAH) in D2O. The positively charged polyelectrolyte molecules interact with the lipid bilayers and induce a drastic increase in their d-spacing by a factor of ~4. Temperature, time, and pH influence the swollen interfacial lipid linings. From our study, we conclude that electrostatic interactions introduced by the adsorbed PAH are the main cause for the drastic swelling of the lipid coatings. The DMPC membrane stacks do not detach from their solid support at T > Tm. Steric interactions, also introduced by the PAH molecules, are held responsible for the stabilizing effect. We believe that this novel system offers great potential for fundamental studies of biomembrane properties, keeping the membrane’s natural fluidity and freedom, decoupled from a solid support at physiological conditions. PMID:26703746

  8. Structure/property relationships in polymer membranes for water purification and energy applications

    NASA Astrophysics Data System (ADS)

    Geise, Geoffrey

    Providing sustainable supplies of purified water and energy is a critical global challenge for the future, and polymer membranes will play a key role in addressing these clear and pressing global needs for water and energy. Polymer membrane-based processes dominate the desalination market, and polymer membranes are crucial components in several rapidly developing power generation and storage applications that rely on membranes to control rates of water and/or ion transport. Much remains unknown about the influence of polymer structure on intrinsic water and ion transport properties, and these relationships must be developed to design next generation polymer membrane materials. For desalination applications, polymers with simultaneously high water permeability and low salt permeability are desirable in order to prepare selective membranes that can efficiently desalinate water, and a tradeoff relationship between water/salt selectivity and water permeability suggests that attempts to prepare such materials should rely on approaches that do more than simply vary polymer free volume. One strategy is to functionalize hydrocarbon polymers with fixed charge groups that can ionize upon exposure to water, and the presence of charged groups in the polymer influences transport properties. Additionally, in many emerging energy applications, charged polymers are exposed to ions that are very different from sodium and chloride. Specific ion effects have been observed in charged polymers, and these effects must be understood to prepare charged polymers that will enable emerging energy technologies. This presentation discusses research aimed at further understanding fundamental structure/property relationships that govern water and ion transport in charged polymer films considered for desalination and electric potential field-driven applications that can help address global needs for clean water and energy.

  9. Water purification by reverse osmosis using heterocyclic polymer membranes

    NASA Technical Reports Server (NTRS)

    Scott, H.

    1972-01-01

    Pyrrone (polyimidazopyrrolone) polymers are a new class of thermally stable, radiation and chemical resistant aromatic-heterocyclic polymers featuring a greater chemical and mechanical durability than cellulose acetate.

  10. Searching for low percolation thresholds within amphiphilic polymer membranes: The effect of side chain branching

    NASA Astrophysics Data System (ADS)

    Dorenbos, G.

    2015-06-01

    Percolation thresholds for solvent diffusion within hydrated model polymeric membranes are derived from dissipative particle dynamics in combination with Monte Carlo (MC) tracer diffusion calculations. The polymer backbones are composed of hydrophobic A beads to which at regular intervals Y-shaped side chains are attached. Each side chain is composed of eight A beads and contains two identical branches that are each terminated with a pendant hydrophilic C bead. Four types of side chains are considered for which the two branches (each represented as [C], [AC], [AAC], or [AAAC]) are splitting off from the 8th, 6th, 4th, or 2nd A bead, respectively. Water diffusion through the phase separated water containing pore networks is deduced from MC tracer diffusion calculations. The percolation threshold for the architectures containing the [C] and [AC] branches is at a water volume fraction of ˜0.07 and 0.08, respectively. These are much lower than those derived earlier for linear architectures of various side chain length and side chain distributions. Control of side chain architecture is thus a very interesting design parameter to decrease the percolation threshold for solvent and proton transports within flexible amphiphilic polymer membranes.

  11. Searching for low percolation thresholds within amphiphilic polymer membranes: The effect of side chain branching

    SciTech Connect

    Dorenbos, G.

    2015-06-14

    Percolation thresholds for solvent diffusion within hydrated model polymeric membranes are derived from dissipative particle dynamics in combination with Monte Carlo (MC) tracer diffusion calculations. The polymer backbones are composed of hydrophobic A beads to which at regular intervals Y-shaped side chains are attached. Each side chain is composed of eight A beads and contains two identical branches that are each terminated with a pendant hydrophilic C bead. Four types of side chains are considered for which the two branches (each represented as [C], [AC], [AAC], or [AAAC]) are splitting off from the 8th, 6th, 4th, or 2nd A bead, respectively. Water diffusion through the phase separated water containing pore networks is deduced from MC tracer diffusion calculations. The percolation threshold for the architectures containing the [C] and [AC] branches is at a water volume fraction of ∼0.07 and 0.08, respectively. These are much lower than those derived earlier for linear architectures of various side chain length and side chain distributions. Control of side chain architecture is thus a very interesting design parameter to decrease the percolation threshold for solvent and proton transports within flexible amphiphilic polymer membranes.

  12. Enhanced ethylene separation and plasticization resistance in polymer membranes incorporating metal-organic framework nanocrystals

    NASA Astrophysics Data System (ADS)

    Bachman, Jonathan E.; Smith, Zachary P.; Li, Tao; Xu, Ting; Long, Jeffrey R.

    2016-08-01

    The implementation of membrane-based separations in the petrochemical industry has the potential to reduce energy consumption significantly relative to conventional separation processes. Achieving this goal, however, requires the development of new membrane materials with greater selectivity, permeability and stability than available at present. Here, we report composite materials consisting of nanocrystals of metal-organic frameworks dispersed within a high-performance polyimide, which can exhibit enhanced selectivity for ethylene over ethane, greater ethylene permeability and improved membrane stability. Our results suggest that framework-polymer interactions reduce chain mobility of the polymer while simultaneously boosting membrane separation performance. The increased stability, or plasticization resistance, is expected to improve membrane utility under real process conditions for petrochemical separations and natural gas purification. Furthermore, this approach can be broadly applied to numerous polymers that encounter aggressive environments, potentially making gas separations possible that were previously inaccessible to membranes.

  13. Enhanced ethylene separation and plasticization resistance in polymer membranes incorporating metal-organic framework nanocrystals.

    PubMed

    Bachman, Jonathan E; Smith, Zachary P; Li, Tao; Xu, Ting; Long, Jeffrey R

    2016-08-01

    The implementation of membrane-based separations in the petrochemical industry has the potential to reduce energy consumption significantly relative to conventional separation processes. Achieving this goal, however, requires the development of new membrane materials with greater selectivity, permeability and stability than available at present. Here, we report composite materials consisting of nanocrystals of metal-organic frameworks dispersed within a high-performance polyimide, which can exhibit enhanced selectivity for ethylene over ethane, greater ethylene permeability and improved membrane stability. Our results suggest that framework-polymer interactions reduce chain mobility of the polymer while simultaneously boosting membrane separation performance. The increased stability, or plasticization resistance, is expected to improve membrane utility under real process conditions for petrochemical separations and natural gas purification. Furthermore, this approach can be broadly applied to numerous polymers that encounter aggressive environments, potentially making gas separations possible that were previously inaccessible to membranes. PMID:27064528

  14. Selective transport of Fe(III) using ionic imprinted polymer (IIP) membrane particle

    NASA Astrophysics Data System (ADS)

    Djunaidi, Muhammad Cholid; Jumina, Siswanta, Dwi; Ulbricht, Mathias

    2015-12-01

    The membrane particles was prepared from polyvinyl alcohol (PVA) and polymer IIP with weight ratios of 1: 2 and 1: 1 using different adsorbent templates and casting thickness. The permeability of membrane towards Fe(III) and also mecanism of transport were studied. The selectivity of the membrane for Fe(III) was studied by performing adsorption experiments also with Cr(III) separately. In this study, the preparation of Ionic Imprinted Polymer (IIP) membrane particles for selective transport of Fe (III) had been done using polyeugenol as functional polymer. Polyeugenol was then imprinted with Fe (III) and then crosslinked with PEGDE under alkaline condition to produce polyeugenol-Fe-PEGDE polymer aggregates. The agrregates was then crushed and sieved using mesh size of 80 and the powder was then used to prepare the membrane particles by mixing it with PVA (Mr 125,000) solution in 1-Methyl-2-pyrrolidone (NMP) solvent. The membrane was obtained after casting at a speed of 25 m/s and soaking in NaOH solution overnight. The membrane sheet was then cut and Fe(III) was removed by acid to produce IIP membrane particles. Analysis of the membrane and its constituent was done by XRD, SEM and size selectivity test. Experimental results showed the transport of Fe(III) was faster with the decrease of membrane thickness, while the higher concentration of template ion correlates with higher Fe(III) being transported. However, the transport of Fe(III) was slower for higher concentration of PVA in the membrane. IImparticles works through retarded permeation mechanism, where Fe(III) was bind to the active side of IIP. The active side of IIP membrane was dominated by the -OH groups. The selectivity of all IIP membranes was confirmed as they were all unable to transport Cr (III), while NIP (Non-imprinted Polymer) membrane was able transport Cr (III).

  15. Honeycomb-like porous gel polymer electrolyte membrane for lithium ion batteries with enhanced safety.

    PubMed

    Zhang, Jinqiang; Sun, Bing; Huang, Xiaodan; Chen, Shuangqiang; Wang, Guoxiu

    2014-01-01

    Lithium ion batteries have shown great potential in applications as power sources for electric vehicles and large-scale energy storage. However, the direct uses of flammable organic liquid electrolyte with commercial separator induce serious safety problems including the risk of fire and explosion. Herein, we report the development of poly(vinylidene difluoride-co-hexafluoropropylene) polymer membranes with multi-sized honeycomb-like porous architectures. The as-prepared polymer electrolyte membranes contain porosity as high as 78%, which leads to the high electrolyte uptake of 86.2 wt%. The PVDF-HFP gel polymer electrolyte membranes exhibited a high ionic conductivity of 1.03 mS cm(-1) at room temperature, which is much higher than that of commercial polymer membranes. Moreover, the as-obtained gel polymer membranes are also thermally stable up to 350 °C and non-combustible in fire (fire-proof). When applied in lithium ion batteries with LiFePO4 as cathode materials, the gel polymer electrolyte demonstrated excellent electrochemical performances. This investigation indicates that PVDF-HFP gel polymer membranes could be potentially applicable for high power lithium ion batteries with the features of high safety, low cost and good performance. PMID:25168687

  16. Honeycomb-like porous gel polymer electrolyte membrane for lithium ion batteries with enhanced safety

    NASA Astrophysics Data System (ADS)

    Zhang, Jinqiang; Sun, Bing; Huang, Xiaodan; Chen, Shuangqiang; Wang, Guoxiu

    2014-08-01

    Lithium ion batteries have shown great potential in applications as power sources for electric vehicles and large-scale energy storage. However, the direct uses of flammable organic liquid electrolyte with commercial separator induce serious safety problems including the risk of fire and explosion. Herein, we report the development of poly(vinylidene difluoride-co-hexafluoropropylene) polymer membranes with multi-sized honeycomb-like porous architectures. The as-prepared polymer electrolyte membranes contain porosity as high as 78%, which leads to the high electrolyte uptake of 86.2 wt%. The PVDF-HFP gel polymer electrolyte membranes exhibited a high ionic conductivity of 1.03 mS cm-1 at room temperature, which is much higher than that of commercial polymer membranes. Moreover, the as-obtained gel polymer membranes are also thermally stable up to 350°C and non-combustible in fire (fire-proof). When applied in lithium ion batteries with LiFePO4 as cathode materials, the gel polymer electrolyte demonstrated excellent electrochemical performances. This investigation indicates that PVDF-HFP gel polymer membranes could be potentially applicable for high power lithium ion batteries with the features of high safety, low cost and good performance.

  17. Honeycomb-like porous gel polymer electrolyte membrane for lithium ion batteries with enhanced safety

    PubMed Central

    Zhang, Jinqiang; Sun, Bing; Huang, Xiaodan; Chen, Shuangqiang; Wang, Guoxiu

    2014-01-01

    Lithium ion batteries have shown great potential in applications as power sources for electric vehicles and large-scale energy storage. However, the direct uses of flammable organic liquid electrolyte with commercial separator induce serious safety problems including the risk of fire and explosion. Herein, we report the development of poly(vinylidene difluoride-co-hexafluoropropylene) polymer membranes with multi-sized honeycomb-like porous architectures. The as-prepared polymer electrolyte membranes contain porosity as high as 78%, which leads to the high electrolyte uptake of 86.2 wt%. The PVDF-HFP gel polymer electrolyte membranes exhibited a high ionic conductivity of 1.03 mS cm−1 at room temperature, which is much higher than that of commercial polymer membranes. Moreover, the as-obtained gel polymer membranes are also thermally stable up to 350°C and non-combustible in fire (fire-proof). When applied in lithium ion batteries with LiFePO4 as cathode materials, the gel polymer electrolyte demonstrated excellent electrochemical performances. This investigation indicates that PVDF-HFP gel polymer membranes could be potentially applicable for high power lithium ion batteries with the features of high safety, low cost and good performance. PMID:25168687

  18. Synthetic Oral Mucin Mimic from Polymer Micelle Networks

    PubMed Central

    2015-01-01

    Mucin networks are formed in the oral cavity by complexation of glycoproteins with other salivary proteins, yielding a hydrated lubricating barrier. The function of these networks is linked to their structural, chemical, and mechanical properties. Yet, as these properties are interdependent, it is difficult to tease out their relative importance. Here, we demonstrate the ability to recreate the fibrous like network through a series of complementary rinses of polymeric worm-like micelles, resulting in a 3-dimensional (3D) porous network that can be deposited layer-by-layer onto any surface. In this work, stability, structure, and microbial capture capabilities were evaluated as a function of network properties. It was found that network structure alone was sufficient for bacterial capture, even with networks composed of the adhesion-resistant polymer, poly(ethylene glycol). The synthetic networks provide an excellent, yet simple, means of independently characterizing mucin network properties (e.g., surface chemistry, stiffness, and pore size). PMID:24992241

  19. Polymers.

    ERIC Educational Resources Information Center

    Tucker, David C.

    1986-01-01

    Presents an open-ended experiment which has students exploring polymer chemistry and reverse osmosis. This activity involves construction of a polymer membrane, use of it in a simple osmosis experiment, and application of its principles in solving a science-technology-society problem. (ML)

  20. Novel Ceramic-Polymer Composite Membranes for the Separation of Hazardous Liquid Waste

    SciTech Connect

    Yoram Cohen

    2001-12-01

    The present project was conceived to address the need for robust yet selective membranes suitable for operating in harsh ph, solvent, and temperature environments. An important goal of the project was to develop a membrane chemical modification technology that would allow one to tailor-design membranes for targeted separation tasks. The method developed in the present study is based on the process of surface graft polymerization. Using essentially the same base technology of surface modification the research was aimed at demonstrating that improved membranes can be designed for both pervaporation separation and ultrafiltration. In the case of pervaporation, the present study was the first to demonstrate that pervaporation can be achieved with ceramic support membranes modified with an essentially molecular layer of terminally anchored polymer chains. The main advantage of the above approach, relative to other proposed membranes, is that the separating polymer layer is covalently attached to the ceramic support. Therefore, such membranes have a potential use in organic-organic separations where the polymer can swell significantly yet membrane robustness is maintained due to the chemical linkage of the chains to be inorganic support. The above membrane technology was also useful in developing fouling resistant ultrafiltration membranes. The prototype membrane developed in the project was evaluated for the treatment of oil-in-water microemulsions, demonstrating lack of irreversible fouling common with commercial membranes.

  1. Flash freezing route to mesoporous polymer nanofibre networks.

    PubMed

    Samitsu, Sadaki; Zhang, Rui; Peng, Xinsheng; Krishnan, Mohan Raj; Fujii, Yoshihisa; Ichinose, Izumi

    2013-01-01

    There are increasing requirements worldwide for advanced separation materials with applications in environmental protection processes. Various mesoporous polymeric materials have been developed and they are considered as potential candidates. It is still challenging, however, to develop economically viable and durable separation materials from low-cost, mass-produced materials. Here we report the fabrication of a nanofibrous network structure from common polymers, based on a microphase separation technique from frozen polymer solutions. The resulting polymer nanofibre networks exhibit large free surface areas, exceeding 300 m(2) g(-1), as well as small pore radii as low as 1.9 nm. These mesoporous polymer materials are able to rapidly adsorb and desorb a large amount of carbon dioxide and are also capable of condensing organic vapours. Furthermore, the nanofibres made of engineering plastics with high glass transition temperatures over 200 °C exhibit surprisingly high, temperature-dependent adsorption of organic solvents from aqueous solution. PMID:24145702

  2. Polymer electrolyte membrane fuel cells for communication applications

    NASA Astrophysics Data System (ADS)

    Chu, Deryn; Jiang, R.; Gardner, K.; Jacobs, R.; Schmidt, J.; Quakenbush, T.; Stephens, J.

    An advanced portable power source using a 50 Watt (PPS-50) polymer electrolyte membrane cell EMFC) system was developed by Ball Aerospace under the US Army, Defense Advanced Research Project Agency (DARPA) and the Office Special Technology (OST) joint program. The PEMFC system was designed as required for commercial and military applications. The system as evaluated extensively under different environmental temperatures and humidity conditions. The thermal behavior and discharge performances of the PEMFC system at different discharge currents, temperatures and relative humidities were also investigated. The temperature range was from -10 to 50°C and the relative humidity (r.h.) from 10 to 90%. The PPS-50 system can provide a normal power output about 50 W at 12 V, while the peak power output can reach approximately 65 W (11 V, 6 A). The water production efficiency from the cathode was approximately 70%, and the residual 30% diffused to the anode side. The system was also used to power PRC-119 radios for communication applications, and it performed extremely well during the retransmission site test, operating continuously for over 25 h.

  3. Radiation initiated grafting onto fluoro polymers for membrane preparation

    NASA Astrophysics Data System (ADS)

    El-Assy, N. B.; Dessouki, A. M.

    The radiation initiating grafting of acrylamide (AAm) onto poly(tetrafluoroethylene/ hexafluoropropylene/vinylidene fluoride), TFB, films using the post-radiation grafting technique has been investigated. The factors affecting the grafting process such as radiation dose, dose rate, monomer concentration and temperature on the grafting yield were studied. It was found that the grafting yield is strongly dependent on the dose but independent on the dose rate. The dependence of the grafting rate on monomer concentration was found to be of 1.44 order. The results showed a steady increase of the initial grafting rate with temperature, whereas the final grafting yield passes a maximum around 45°C. The Arrhenius plot reveals two straight lines with different slope intersecting around 35°C. The overall activation energy for this grafting system was calculated and found to be 16.5 and 32.4 kcal/mol above and below 35°C, respectively. This behaviour is presumably correlated to a glass transition of the trunk polymer arising from amorphous material under restraint by crystallites. Some properties of the grafted films such a specific electric resistance, water uptake, mechanical properties and chemical and thermal stability were investigated. An improvement in these properties was observed which makes possible the use of these membranes in some practical applications.

  4. Polymer Membranes with Vertically Oriented Pores Constructed by 2D Freezing at Ambient Temperature.

    PubMed

    Liang, Hong-Qing; Ji, Ke-Jia; Zha, Li-Yun; Hu, Wen-Bing; Ou, Yang; Xu, Zhi-Kang

    2016-06-01

    Polymer membranes with well-controlled and vertically oriented pores are of great importance in the applications for water treatment and tissue engineering. On the basis of two-dimensional solvent freezing, we report environmentally friendly facile fabrication of such membranes from a broad spectrum of polymer resources including poly(vinylidene fluoride), poly(l-lactic acid), polyacrylonitrile, polystyrene, polysulfone and polypropylene. Dimethyl sulfone, diphenyl sulfone, and arachidic acid are selected as green solvents crystallized in the polymer matrices under two-dimensional temperature gradients induced by water at ambient temperature. Parallel Monte Carlo simulations of the lattice polymers demonstrate that the directional process is feasible for each polymer holding suitable interaction with a corresponding solvent. As a typical example of this approach, poly(vinylidene fluoride) membranes exhibit excellent tensile strength, high optical transparence, and outstanding separation performance for the mixtures of yeasts and lactobacilli. PMID:27188247

  5. Quantitative Measurement of Cationic Polymer Vector and Polymer-pDNA Polyplex Intercalation into the Cell Plasma Membrane.

    PubMed

    Vaidyanathan, Sriram; Anderson, Kevin B; Merzel, Rachel L; Jacobovitz, Binyamin; Kaushik, Milan P; Kelly, Christina N; van Dongen, Mallory A; Dougherty, Casey A; Orr, Bradford G; Banaszak Holl, Mark M

    2015-06-23

    Cationic gene delivery agents (vectors) are important for delivering nucleotides, but are also responsible for cytotoxicity. Cationic polymers (L-PEI, jetPEI, and G5 PAMAM) at 1× to 100× the concentrations required for translational activity (protein expression) induced the same increase in plasma membrane current of HEK 293A cells (30-50 nA) as measured by whole cell patch-clamp. This indicates saturation of the cell membrane by the cationic polymers. The increased currents induced by the polymers are not reversible for over 15 min. Irreversibility on this time scale is consistent with a polymer-supported pore or carpet model and indicates that the cell is unable to clear the polymer from the membrane. For polyplexes, although the charge concentration was the same (at N/P ratio of 10:1), G5 PAMAM and jetPEI polyplexes induced a much larger current increase (40-50 nA) than L-PEI polyplexes (<20 nA). Both free cationic lipid and lipid polyplexes induced a lower increase in current than cationic polymers (<20 nA). To quantify the membrane bound material, partition constants were measured for both free vectors and polyplexes into the HEK 293A cell membrane using a dye influx assay. The partition constants of free vectors increased with charge density of the vectors. Polyplex partition constants did not show such a trend. The long lasting cell plasma permeability induced by exposure to the polymer vectors or the polyplexes provides a plausible mechanism for the toxicity and inflammatory response induced by exposure to these materials. PMID:25952271

  6. Obtention and evaluation of polyethylene-based solid polymer electrolyte membranes fro hydrogen production

    NASA Astrophysics Data System (ADS)

    Masson, J. P.; Molina, R.; Roth, E.; Gaussens, G.; Lemaire, F.

    The fabrication and testing of a polyethylene-based solid polymer electrolyte for use in hydrogen production by water electrolysis are discussed. The fabrication process involves the radiation grafting of styrene groups onto a polyethylene matrix, followed by the chemical sulphonation of the resulting polymer. The membrane produced has exhibited resistivities as low as 60 ohm cm for a 1-mm thickness, and other properties of the same order of magnitude as those of the commercially available but more expensive Nafion 014 membrane. Life tests carried out at a current density of 2 kA/sq m in single-cell modules with 10-sq cm active surface have revealed no noticeable degradation in membrane mechanical or electrical properties after 3000 hours for membranes reinforced by an organic polymer fabric. The development of an electrolyzer specifically designed for operation with a solid polymer electrolyte is currently under way.

  7. Structure of highly rigid ionic polymers from single molecules to membranes

    NASA Astrophysics Data System (ADS)

    He, Lilin; Cornelius, Christopher J.

    2005-03-01

    The structure of ionic polymers in solutions and in their solid state is governed by the segregation to hydrophilic and hydrophobic regions. Very rigid backbones with persistence lengths much larger than the size of the monomer limit the segregation affecting the resulting structure and dynamics of the polymers. Using a newly synthesized para phenylene based sulfonated polymer with a potential to serve as a polymeric electrolytic membrane for fuel cell applications, we followed the structure of highly rigid ionic polymers from a single molecule to a water swollen membranes using small angle neutron scattering and AFM/TEM techniques. AFM and TEM images show that the dry membranes have domains with a diameter from 30 nm to 70nm. Small angle neutron scattering probes the smaller structure in the membranes from dry to swollen states. Fitting to Teubner-Strey model of SANS data indicates the bi-continuous phases were formed with water and ethanol despite the rigidity of the backbone.

  8. Fluorinated Azobenzenes for Shape-Persistent Liquid Crystal Polymer Networks.

    PubMed

    Iamsaard, Supitchaya; Anger, Emmanuel; Aßhoff, Sarah Jane; Depauw, Alexis; Fletcher, Stephen P; Katsonis, Nathalie

    2016-08-16

    Liquid crystal polymer networks respond with an anisotropic deformation to a range of external stimuli. When doped with molecular photoswitches, these materials undergo complex shape modifications under illumination. As the deformations are reversed when irradiation stops, applications where the activated shape is required to have thermal stability have been precluded. Previous attempts to incorporate molecular switches into thermally stable photoisomers were unsuccessful at photogenerating macroscopic shapes that are retained over time. Herein, we show that to preserve photoactivated molecular deformation on the macroscopic scale, it is important not only to engineer the thermal stability of the photoswitch but also to adjust the cross-linking density in the polymer network and to optimize the molecular orientations in the material. Our strategy resulted in materials containing fluorinated azobenzenes that retain their photochemical shape for more than eight days, which constitutes the first demonstration of long-lived photomechanical deformation in liquid-crystal polymer networks. PMID:27430357

  9. Ti3C2Tx Filler Effect on the Proton Conduction Property of Polymer Electrolyte Membrane.

    PubMed

    Liu, Yahua; Zhang, Jiakui; Zhang, Xiang; Li, Yifan; Wang, Jingtao

    2016-08-10

    Conductive polymer electrolyte membranes are increasingly attractive for a wide range of applications in hydrogen-relevant devices, for instance hydrogen fuel cells. In this study, two-dimensional Ti3C2Tx, a typical representative of the recently developed MXene family, is synthesized and employed as a universal filler for its features of large specific surface area, high aspect ratio, and sufficient terminated -OH groups. The Ti3C2Tx is incorporated into polymer matrix to explore its function on membrane microstructure and proton conduction property. Both phase-separated (acidic Nafion and sulfonated poly(ether ether ketone)) and non-phase-separated (basic chitosan) polymers are utilized as membrane matrixes. The microstructures, physicochemical properties, and proton conduction properties of the membranes are extensively investigated. It is demonstrated that Ti3C2Tx generates significant promotion effect on proton conduction of the composite membrane by facilitating both vehicle-type and Grotthuss-type proton transfer, yielding several times increased proton conductivity for every polymer-based composite membrane under various conditions, and the composite membrane achieves elevated hydrogen fuel cell performance. The stable Ti3C2Tx also reinforces the thermal and mechanical stabilities of these composite membranes. Since the MXene family includes more than 70 members, this exploration is expected to open up new perspectives for expanding their applications, especially as membrane modifiers and proton conductors. PMID:27430190

  10. Effect of polymer on the elasticity of surfactant membranes: a light scattering study.

    PubMed

    Iñiguez-Palomares, Ramón; Acuña-Campa, Heriberto; Maldonado, Amir

    2011-07-01

    We have performed a dynamic light-scattering (DLS) investigation of the effect of a water-soluble polymer, polyethylene glycol (PEG), on the bending elastic modulus κ of surfactant membranes. The polymer, in concentrations ranging from 0 to 8 g/L (0 to 0.4 mM), was incorporated into the solvent of sponge phases of the sodium dodecyl sulfate (SDS)-hexanol-brine system. PEG adsorbs into the SDS membranes. The correlation functions of the polymer-doped sponge phases displayed a stretched-exponential decay, appropriately described by the Zilman-Granek (Z-G) theory for fluctuating membranes. The dynamics of the surfactant bilayers was slowed down by the addition of the polymer: Increasing PEG concentrations increase the DLS relaxation times. From the Z-G model we extracted the membrane-bending elastic modulus, as a function of polymer concentration, C(PEG) = κ increases with C(PEG), a behavior opposite to that expected from available models for the interaction between fluid membranes and adsorbing polymers. Our results suggest that the polymer penetrates to some extent the surfactant bilayers. PMID:21867181

  11. Effect of polymer on the elasticity of surfactant membranes: A light scattering study

    NASA Astrophysics Data System (ADS)

    Iñiguez-Palomares, Ramón; Acuña-Campa, Heriberto; Maldonado, Amir

    2011-07-01

    We have performed a dynamic light-scattering (DLS) investigation of the effect of a water-soluble polymer, polyethylene glycol (PEG), on the bending elastic modulus κ of surfactant membranes. The polymer, in concentrations ranging from 0 to 8 g/L (0 to 0.4 mM), was incorporated into the solvent of sponge phases of the sodium dodecyl sulfate (SDS)-hexanol-brine system. PEG adsorbs into the SDS membranes. The correlation functions of the polymer-doped sponge phases displayed a stretched-exponential decay, appropriately described by the Zilman-Granek (Z-G) theory for fluctuating membranes. The dynamics of the surfactant bilayers was slowed down by the addition of the polymer: Increasing PEG concentrations increase the DLS relaxation times. From the Z-G model we extracted the membrane-bending elastic modulus, as a function of polymer concentration, CPEG=κ increases with CPEG, a behavior opposite to that expected from available models for the interaction between fluid membranes and adsorbing polymers. Our results suggest that the polymer penetrates to some extent the surfactant bilayers.

  12. Application of bias voltage to tune the resonant frequency of membrane-based electroactive polymer energy harvesters

    NASA Astrophysics Data System (ADS)

    Dong, Lin; Grissom, Michael; Fisher, Frank T.

    2016-05-01

    Vibration-based energy harvesting has been widely investigated to as a means to generate low levels of electrical energy for applications such as wireless sensor networks. However, for optimal performance it is necessary to ensure that resonant frequencies of the device match the ambient vibration frequencies for maximum energy harvested. Here a novel resonant frequency tuning approach is proposed by applying a bias voltage to a pre-stretched electroactive polymer (EAP) membrane, such that the resulting changes in membrane tension can tune the device to match the environmental vibration source. First, a material model which accounts for the change in properties due to the pre-stretch of a VHB 4910 EAP membrane is presented. The effect of the bias voltage on the EAP membrane, which induces an electrostatic pressure and corresponding reduction in membrane thickness, are then determined. The FEM results from ANSYS agree well with an analytical hyperelastic model of the activation response of the EAP membrane. Lastly, through a mass-loaded circular membrane vibration model, the effective resonant frequency of the energy harvester can be determined as a function of changes in membrane tension due to the applied bias voltage. In the case of an EAP membrane, pre-stretch contributes to the pre-stretch stiffness of the system while the applied bias voltage contributes to a change in bias voltage stiffness of the membrane. Preliminary experiments verified the resonant frequencies corresponding to the bias voltages predicted from the appropriate models. The proposed bias voltage tuning approach for the EAP membrane may provide a novel tuning strategy to enable energy harvesting from various ambient vibration sources in various application environments.

  13. Morphology and Proton Transport in Sulfonated Block Copolymer and Mesoporous Polymer Electrolyte Membranes

    NASA Astrophysics Data System (ADS)

    Chen, Chelsea; Wong, David; Beers, Keith; Balsara, Nitash

    2013-03-01

    In an effort to understand the fundamentals of proton transport in polymer electrolyte membranes (PEMs), we have developed a series of poly(styrene-b-ethylene-b-styrene) (SES) membranes. The SES membranes were subsequently sulfonated to yield proton conducting S-SES membranes. We examine the effects of sulfonation level, temperature and thermal history on the morphology of S-SES membranes in both dry and hydrated states. The effects of these parameters on water uptake and proton transport characteristics of the membranes are also examined. Furthermore, building upon the strategy we deployed in sulfonating the SES membranes, we fabricated mesoporous S-SES membranes, with pores lined up with the proton conducting channels. These membranes have three distinct phases: structural block, proton-conducting block, and void. We examine the effects of pore size, domain structure and sulfonation level on water uptake and proton conductivity of the mesoporous PEMs at different temperatures. This work is funded by Department of Energy.

  14. The mechanics of network polymers with thermally reversible linkages

    NASA Astrophysics Data System (ADS)

    Long, Kevin N.

    2014-02-01

    Network polymers with thermally reversible linkages include functionalities that continuously break and form covalent bonds. These processes dynamically change the network connectivity, which produces three distinct behaviors compared with conventional thermosetting polymers (in which the network connectivity is static): permanent shape evolution in the rubbery state; dependence of the number density of chains and associated thermal and mechanical properties on temperature and chemical composition; and a gel-point transition temperature above which the connectivity of the network falls below the percolation threshold, and the material response changes from a solid to liquid. This last property allows such materials to be non-mechanically removed, which is an attractive material capability for encapsulation in specialized electronics packaging applications wherein system maintenance is required. Given their complex, multi-physics behavior, appropriate simulation tools are needed to aid in their use.

  15. Direct detection of RDX vapor using a conjugated polymer network.

    PubMed

    Gopalakrishnan, Deepti; Dichtel, William R

    2013-06-01

    1,3,5-Trinitroperhydro-1,3,5-triazine (RDX) is a principal component of plastic explosives used in acts of terrorism and within improvised explosive devices, among others. Approaches to detect RDX compatible with remote, "stand-off" sampling that do not require preconcentration strategies, such as the swabs commonly employed in airports, will benefit military and civilian security. Such detection remains a significant challenge because RDX is 10(3) less volatile than 1,3,5-trinitrotoluene (TNT), corresponding to a parts-per-trillion vapor pressure under ambient conditions. Therefore, while fluorescence quenching of conjugated polymers is sufficiently sensitive to detect TNT vapors, RDX vapor detection is undemonstrated. Here we report a cross-linked phenylene vinylene polymer network whose fluorescence is quenched by trace amounts of RDX introduced from solution or the vapor phase. Fluorescence quenching is reduced, but remains significant, when partially degraded RDX is employed, suggesting that the polymer responds to RDX itself. The polymer network also responds to TNT and PETN similarly introduced from solution or the vapor phase. Pure solvents, volatile amines, and the outgassed vapors from lipstick or sunscreen do not quench polymer fluorescence. The established success of TNT sensors based on fluorescence quenching makes this a material of interest for real-world explosive sensors and will motivate further interest in cross-linked polymers and framework materials for sensing applications. PMID:23641956

  16. Competing dynamic phases of active polymer networks

    NASA Astrophysics Data System (ADS)

    Freedman, Simon; Banerjee, Shiladitya; Dinner, Aaron R.

    Recent experiments on in-vitro reconstituted assemblies of F-actin, myosin-II motors, and cross-linking proteins show that tuning local network properties can changes the fundamental biomechanical behavior of the system. For example, by varying cross-linker density and actin bundle rigidity, one can switch between contractile networks useful for reshaping cells, polarity sorted networks ideal for directed molecular transport, and frustrated networks with robust structural properties. To efficiently investigate the dynamic phases of actomyosin networks, we developed a coarse grained non-equilibrium molecular dynamics simulation of model semiflexible filaments, molecular motors, and cross-linkers with phenomenologically defined interactions. The simulation's accuracy was verified by benchmarking the mechanical properties of its individual components and collective behavior against experimental results at the molecular and network scales. By adjusting the model's parameters, we can reproduce the qualitative phases observed in experiment and predict the protein characteristics where phase crossovers could occur in collective network dynamics. Our model provides a framework for understanding cells' multiple uses of actomyosin networks and their applicability in materials research. Supported by the Department of Defense (DoD) through the National Defense Science & Engineering Graduate Fellowship (NDSEG) Program.

  17. Fabrication and Testing of a Bi-Conductive Polymer Membrane Fuel Cell

    NASA Astrophysics Data System (ADS)

    Hamel, S.; Tsukamoto, T.; Tanaka, T.; Fréchette, L. G.

    2014-11-01

    This paper reports the fabrication process and testing of a bi-conductive polymer membrane (BCPM) fuel cell that integrates lateral current collectors on both sides with an ionic conductive path through the membrane. The new membrane shows major advantages over standard Nafion® membranes used in Polymer Electrolyte Fuel Cells (PEMFCs). In addition to being mechanically stable when wet, the flexible BCPM integrates efficient thin film current collectors (ICCs) on an ionic conductive membrane with a high active area ratio. Also, ICCs leave all the surface of the electrode free to eventually integrate a more efficient water and gas management system than traditional gas diffusion layers. Moreover, the fabricated membrane has shown superior volumetric power density than standard PEMFC (0.76 vs 0.47 mW/cm2μm).

  18. Proton conducting, high modulus polymer electrolyte membranes by polymerization-induced microphase separation

    NASA Astrophysics Data System (ADS)

    Chopade, Sujay; Hillmyer, Marc; Lodge, Timothy

    Robust solid-state polymer electrolyte membranes (PEMs) are vital for designing next-generation lithium-ion batteries and high-temperature fuel cells. However, the performance of diblock polymer electrolytes is generally limited by poor mechanical stability and network defects in the conducting pathways. We present the in-situ preparation of robust cross-linked PEMs via polymerization-induced microphase separation, and incorporation of protic ionic liquid (IL) into one of the microphase separated domains. The facile design strategy involves a delicate balance between the controlled growth of polystyrene from a poly(ethylene oxide) macro-chain transfer agent (PEO-CTA) and simultaneous chemical cross-linking by divinylbenzene in the presence of IL. Small angle X-ray scattering and transmission electron microscopy confirmed the formation of a disordered structure with bicontinuous morphology and a characteristic domain size of order 20 nm. The long-range continuity of the PEO/protic IL conducting nanochannels and cross-linked polystyrene domains imparts high thermal and mechanical stability to the PEMs, with elastic modulus approaching 10 MPa and a high ionic conductivity of 15 mS/cm at 180 °C.

  19. Influence of polymer network in polymer-stabilized ferroelectric liquid crystals and its direct observation using a confocal microscope

    NASA Astrophysics Data System (ADS)

    Petkovšek, R.; Pirš, J.; Kralj, S.; Čopič, M.; Šuput, D.

    2006-01-01

    The paper presents the analysis of the three-dimensional polymer network distribution inside the polymer-stabilized ferroelectric liquid-crystal layer based on the laser scanning fluorescence confocal microscopy and a fluorescent dye tagging of the polymer. The studies of polymer-stabilized ferroelectric liquid-crystal structures described in this paper are focused on the comparison of the influence of polymer network in case that the polymerization is initiated in the chevron as well as in the quasibookshelf liquid-crystal molecular orientation. In the case of the chevron structure the regular distribution of the polymer network within the layer leads to the monostability of the chevron state. On the other hand the specific distribution of the polymer in the polymer-stabilized quasibookshelf stripe textures leads to the perfect bistability, improved multiplex driving, and analog gray scale capability.

  20. Macro- and microphase separation in multifunctional supramolecular polymer networks

    NASA Astrophysics Data System (ADS)

    Mester, Zoltan; Mohan, Aruna; Fredrickson, Glenn

    2011-03-01

    We develop a field-based model for a binary melt of multifunctional polymers that can reversibly bond to form copolymer networks. The mean-field phase separation behavior of several model networks with heterogeneous bonding is calculated via the random phase approximation (RPA). The extent of bonding between polymers is controlled by specified bond energies. The phase boundary calculated via RPA is the stability limit of the homogeneous disordered phase to coexisting homogeneous macrophases, for low bond strengths, and to microphases, for high bond strengths. An isotropic Lifshitz point separates these two regions along the spindodal boundary. It is demonstrated that higher functionality and higher bond strength suppresses macrophase separation due to greater connectivity between unlike species. Gelation first occurs at a bond strength higher than the Lifshitz point for tri- or higher functional polymer components.

  1. Semi-2-interpenetrating polymer networks of high temperature systems

    NASA Technical Reports Server (NTRS)

    Hanky, A. O.; St. Clair, T. L.

    1985-01-01

    A semi-interpenetrating (semi-IPN) polymer system of the semi-2-IPN type is described in which a polymer of acetylene-terminated imidesulfone (ATPISO2) is cross linked in the presence of polyimidesulfone (PISO2). Six different formulations obtained by mixing of either ATPISO2-1n or ATPISO2-3n with PISO2 in three different proportions were characterized in terms of glass transition temperature, thermooxidative stability, inherent viscosity, and dynamic mechanical properties. Adhesive (lap shear) strength was tested at elevated temperatures on aged samples of adhesive scrim cloth prepared from each resin. Woven graphite (Celion 1000)/polyimide composites were tested for flexural strength, flexural modulus, and shear strength. The network polymers have properties intermediate between those of the component polymers alone, have greatly improved processability over either polyimide, and are able to form good adhesive bonds and composites, making the semi-2-IPN systems superior materials for aerospace structures.

  2. Controlled architecture for improved macromolecular memory within polymer networks.

    PubMed

    DiPasquale, Stephen A; Byrne, Mark E

    2016-08-01

    This brief review analyzes recent developments in the field of living/controlled polymerization and the potential of this technique for creating imprinted polymers with highly structured architecture with macromolecular memory. As a result, it is possible to engineer polymers at the molecular level with increased homogeneity relating to enhanced template binding and transport. Only recently has living/controlled polymerization been exploited to decrease heterogeneity and substantially improve the efficiency of the imprinting process for both highly and weakly crosslinked imprinted polymers. Living polymerization can be utilized to create imprinted networks that are vastly more efficient than similar polymers produced using conventional free radical polymerization, and these improvements increase the role that macromolecular memory can play in the design and engineering of new drug delivery and sensing platforms. PMID:27322505

  3. Morphological analysis of Polyethersulfone/polyvinyl Acetate blend membrane synthesized at various polymer concentrations

    NASA Astrophysics Data System (ADS)

    Hadi, S. H. A. A.; Mannan, H. A.; Mukhtar, H.; Shaharun, M. S.; Murugesan, T.

    2016-06-01

    This paper reports the effect of varying polymer concentration i.e. solvent/polymer ratio on the morphology and gas transport behaviour of polyethersulfone/polyvinyl acetate blend membrane. The solvent used was dimethylformamide, while the manipulated variable was polymer concentration. The concentrations were varied from 75-90 weight % solvent. A homogeneous surface with dense cross-section structure membranes were successfully developed as deduced from FESEM images. The permeability of CO2 and CH4 gases increased with increasing polymer concentration and an improved CO2/CH4 selectivity was observed. These observation made from the characterization justified the applicability of the blend to be synthesized as membrane for gas separation.

  4. Interfacial and Mechanical Characterization of Soft Materials Using Polymer Membranes Geometries

    NASA Astrophysics Data System (ADS)

    Laprade, Evan J.

    Polymer membranes have found their way in to a wide range of applications including selective barriers, protective coatings, packaging, sensors, and medical implants, becom- ing more pervasive in our lives every day. Their importance is derived not only from their unique mechanical and interfacial properties, but also from the versatility of their geometry. In this thesis, several polymer membrane geometries are employed to interfacially and mechanically characterize the properties of soft materials and polymer thin films. This thesis is organized in to two sections, the first deals with interfacial characterization using a membrane contact geometry. The centerpiece of this section, and this thesis, was the development of a sensitive membrane peel test to measure adhesion. A model membrane-contact system was used to evaluate an analytical model of large deformation contact and ultimately develop a simple protocol for measuring an adhesion energy using a membrane peel geometry. A second investigation in the section looked at the multiple harmonic behavior of quartz crystal resonators during contact mechanics experiments. An analytical solution to the radial mass sensitivity function was calculated and compared to experimentally measured sensitivity profiles from growing water drop and membrane contact experiments. The second half of this thesis deals with non-contact membrane geometries for mechanically characterizing two novel polymer membranes. The first is a highly water permeable sulfonated pentablock copolymer, designed for water purification applications. In this work these membranes were mechanically characterized with a biaxial creep test to investigate the affect of sulfonation level and processing conditions on their deformation behavior. Lastly pendant drop membranes were fabricated by ionically crosslinking amphiphilic gradient copolymers at an oil/water interface. These robust, self healing membranes were modeled with both an elastic and liquid

  5. Enhanced Two-Stage Reactive Polymer Network Forming Systems

    PubMed Central

    Nair, Devatha P.; Cramer, Neil B.; McBride, Matthew K.; Gaipa, John C.; Shandas, Robin; Bowman, Christopher N.

    2012-01-01

    In this study, we develop thiol/acrylate two-stage reactive network forming polymer systems that exhibit two distinct and orthogonal stages of curing. Using a thiol-acrylate system with excess acrylate functional groups, a first stage polymer network is formed via a 1 to 1 stoichiometric thiol-acrylate Michael addition reaction (stage 1). At a later point in time, the excess acrylate functional groups are homopolymerized via a photoinitiated free radical polymerization to form a second stage polymer network (stage 2). By varying the monomers within the system as well as the stoichiometery of the thiol to acrylate functional groups, we demonstrate the ability of the two-stage polymer network forming systems to encompass a wide range of properties at the end of both the stage 1 and stage 2 polymerizations. Using urethane di- and hexa-acrylates within the formulations led to two-stage reactive polymeric systems with stage 1 Tgs that ranged from −12 to 30 °C. The systems were then photocured, upon which the Tg of the systems increases by up to 90 °C while also achieving a nearly 20 fold modulus increase. PMID:22798700

  6. Magnetic resonance imaging of solvent transport in polymer networks

    SciTech Connect

    Botto, R.E.; Cody, G.D.

    1995-02-01

    The spectroscopic technique of magnetic resonance imaging (MRI) has recently provided a new window into transport of solvents in polymer networks. Diffusion of solvent as a rate-controlling phenomenon is paramount to understanding transport in many important industrial and biological processes, such as upgrading fossil fuels, film casting and coating, development of photoresists, design of drug-delivery systems, development of solvent resistant polymers, etc. By MRI mapping the migration of solvent molecules through various polymer specimens, researchers Robert Botto and George Cody of Argonne National Laboratory, with support from the Division of Chemical Sciences at DOE, were able to characterize and distinguish between different modes of transport behavior associated with fundamentally different types of polymer systems. The method was applied to rubbers, glassy polymers, and coals. In polymers shown to undergo a glass transition from a rigid to rubbery state, a sharply defined solvent front was observed that propagated through specimens in the manner of a constant velocity shock wave. This behavior was contrasted with a smooth solvent concentration gradient found in polymer systems where no glass transition was observed. The results of this analysis have formed the basis of a new model of anomalous transport in polymeric solids and are helping to ascertain fundamental information on the molecular architectures of these materials.

  7. Possible continuity of subplasmalemmal cytoplasmic network with basement membrane cord network: ultrastructural study.

    PubMed

    Inoue, S

    1995-05-01

    The ultrastructure of the subplasmalemmal cytoplasm of the cell and the associated basement membrane as well as the area of the cell-basement membrane border were observed with high resolution electron microscopy after preparation of the tissues with cryofixation or glutaraldehyde fixation followed by freeze substitution. The subplasmalemmal cytoplasm of the smooth muscle cells of rat epididymal tubules and the podocyte processes of the mouse glomerular visceral epithelium were found to be composed of a fine network of irregular anastomosing strands. This network closely resembled the previously characterized cord network of the basement membrane. The cords are known to be composed of a 1.5 to 3 nm thick core filament made up of type IV collagen which is surrounded by an irregular 'sheath' of other components. The strands in the subplasmalemmal network showed ultrastructural features similar to those of the cord network. Ribbon-like, 4.5 nm wide heparan sulfate proteoglycan 'double tracks' were previously reported to be associated with the cord network. Structures similar in size and appearance to the double tracks were also found in the subplasmalemmal network. At the cell-basement membrane border, the lamina densa of the basement membrane was in contact with the cell without the intervening space of a lamina lucida which was recently found to be an artefact caused by conventional tissue processing. Furthermore, the subplasmalemmal network appeared to be continuous through the plasma membrane, with the cord network of the basement membrane.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:7657717

  8. Polymer blend membranes for CO2 separation from natural gas

    NASA Astrophysics Data System (ADS)

    Mukhtar, H.; Mannan, H. A.; Minh, D.; Nasir, R.; Moshshim, D. F.; Murugesan, T.

    2016-06-01

    Polymeric membranes are dominantly used in industrial gas separation membrane processes. Enhancement in membranes permeability and/or selectivity is a key challenge faced by membrane researchers. The current work represents the effect of poyetherimide blending on separation performance of polysulfone membranes. Polysulfone/poyetherimide (PSF/PEI) blend flat sheet dense membranes were synthesized and tested for permeation analysis of CO2 and CH4 gases at 6, 8 and 10 bar pressure and 25oC temperature. Morphology and thermal properties of membranes were characterized by field emission scanning electron microscope (FESEM) and thermo gravimetric analysis (TGA) respectively. Blend membranes were dense and homogeneous as deduced from FESEM analysis. Thermal stability of synthesized blend membranes was maintained by blending with PEI as characterized by TGA results. Decrease in permeability of both gases was observed by the addition of PEI due to rigidity of PEI chains. Additionally, selectivity of synthesized blend membranes was enhanced by blending PEI and blend membranes show improved selectivity over pure PSF membrane. This new material has the capability to be used as gas separation membrane material.

  9. Initial conditioning of polymer eelectrolyte membrane fuel cell by temperature and potential cycling.

    PubMed

    Bezmalinović, Dario; Radošević, Jagoda; Barbir, Frano

    2015-01-01

    Polymer electrolyte membrane fuel cells need initial conditioning, activation or break-in the first time they are operated after being assembled. During this period performance of the fuel cell improves until it reaches its nominal performance. The exact mechanism of this initial conditioning is not completely understood, but it is assumed that during the conditioning process the polymer membrane, as well as the polymer in the catalyst layer, get humidified, and the number of active catalyst sites increases. Activation procedure proposed here consists of temperature and potential cycling. Temperature cycling is a new approach for the conditioning and the idea is to rapidly cool the running cell at some point to allow the membrane to equilibrate with condensed water which should result in higher intake of water within the membrane. The results show that proposed procedure is better or at least comparable to some conventional procedures for the initial conditioning. PMID:25830963

  10. Experimental studies of siloxane polymers and their elastomeric networks

    SciTech Connect

    Kuo, Chung Mien

    1992-12-31

    Siloxane polymers have been investigated systematically for the purpose of a greater understanding of the structure-property relationships in terms of their synthesis, polymer blends and rubber elasticity of their crosslinked networks. This study includes a variety of topological structures: linear, cyclic and crosslinked networks of poly(dimethylsiloxane) (PDMS) and poly(dimethylco-methylphenylsiloxane) copolymers. Siloxane polymers with a narrow molecular weight distribution were prepared by a series of well-characterized organometallic polymerizations. The reaction conditions and mechanisms for preparing polyorganosiloxane chains and networks using organotin catalyst and promoters were discussed. Experimental evidence shows that formamide was one of the best additives to improve the reactivity of the tin dicarboxylate catalyst, which seems to suggest that the nucleophilic function of the additive was on the Sn atom. Since the PDMS and PMPS are immiscible under most conditions, the miscibility and phase behavior of siloxane blends were studied by a static light scattering t technique. THe influence of molar mass, the topological effect of cyclic and linear structures, the end-group effect, and the configurational isomerism effect on miscibility were examined. Silicon networks of PDMS, PMPS and their copolymers were prepared at room temperature using the crosslinked siloxane homopolymer and copolymer networks at equilibrium swelling in organic solvents and in liquid siloxane oligomers were investigated as function of crosslinking density and composition variation. The resulting interaction parameters for PDMS and PMPS from the swollen siloxane networks in siloxane oligomers individually were compared with those from measurements of the corresponding blend systems. Moreover, the stress-strain behavior of the siloxane polymer networks undergoing uniaxial deformation were evaluated by a stress-strain experiment.

  11. Membrane surface modification via polymer grafting and interfacial polymerization

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Membrane separation is an important technology for separating food ingredients and fractionating high-value substances from food processing by-products. Long-term uses of polymeric membranes in food protein processing are impeded by formation of fouled layers on the membrane surface. Surface modif...

  12. The Effect of Platinum Electrocatalyst on Membrane Degradation in Polymer Electrolyte Fuel Cells.

    PubMed

    Bodner, Merit; Cermenek, Bernd; Rami, Mija; Hacker, Viktor

    2015-01-01

    Membrane degradation is a severe factor limiting the lifetime of polymer electrolyte fuel cells. Therefore, obtaining a deeper knowledge is fundamental in order to establish fuel cells as competitive product. A segmented single cell was operated under open circuit voltage with alternating relative humidity. The influence of the catalyst layer on membrane degradation was evaluated by measuring a membrane without electrodes and a membrane-electrode-assembly under identical conditions. After 100 h of accelerated stress testing the proton conductivity of membrane samples near the anode and cathode was investigated by means of ex situ electrochemical impedance spectroscopy. The membrane sample near the cathode inlet exhibited twofold lower membrane resistance and a resulting twofold higher proton conductivity than the membrane sample near the anode inlet. The results from the fluoride ion analysis have shown that the presence of platinum reduces the fluoride emission rate; which supports conclusions drawn from the literature. PMID:26670258

  13. The Effect of Platinum Electrocatalyst on Membrane Degradation in Polymer Electrolyte Fuel Cells

    PubMed Central

    Bodner, Merit; Cermenek, Bernd; Rami, Mija; Hacker, Viktor

    2015-01-01

    Membrane degradation is a severe factor limiting the lifetime of polymer electrolyte fuel cells. Therefore, obtaining a deeper knowledge is fundamental in order to establish fuel cells as competitive product. A segmented single cell was operated under open circuit voltage with alternating relative humidity. The influence of the catalyst layer on membrane degradation was evaluated by measuring a membrane without electrodes and a membrane-electrode-assembly under identical conditions. After 100 h of accelerated stress testing the proton conductivity of membrane samples near the anode and cathode was investigated by means of ex situ electrochemical impedance spectroscopy. The membrane sample near the cathode inlet exhibited twofold lower membrane resistance and a resulting twofold higher proton conductivity than the membrane sample near the anode inlet. The results from the fluoride ion analysis have shown that the presence of platinum reduces the fluoride emission rate; which supports conclusions drawn from the literature. PMID:26670258

  14. Polymer Solar Cells: Solubility Controls Fiber Network Formation.

    PubMed

    van Franeker, Jacobus J; Heintges, Gaël H L; Schaefer, Charley; Portale, Giuseppe; Li, Weiwei; Wienk, Martijn M; van der Schoot, Paul; Janssen, René A J

    2015-09-16

    The photoactive layer of polymer solar cells is commonly processed from a four-component solution, containing a semiconducting polymer and a fullerene derivative dissolved in a solvent-cosolvent mixture. The nanoscale dimensions of the polymer-fullerene morphology that is formed upon drying determines the solar cell performance, but the fundamental processes that govern the size of the phase-separated polymer and fullerene domains are poorly understood. Here, we investigate morphology formation of an alternating copolymer of diketopyrrolopyrrole and a thiophene-phenyl-thiophene oligomer (PDPPTPT) with relatively long 2-decyltetradecyl (DT) side chains blended with [6,6]-phenyl-C71-butyric acid methyl ester. During solvent evaporation the polymer crystallizes into a fibrous network. The typical width of these fibers is analyzed by quantification of transmission electron microscopic images, and is mainly determined by the solubility of the polymer in the cosolvent and the molecular weight of the polymer. A higher molecular weight corresponds to a lower solubility and film processing results in a smaller fiber width. Surprisingly, the fiber width is not related to the drying rate or the amount of cosolvent. We have made solar cells with fiber widths ranging from 28 to 68 nm and found an inverse relation between fiber width and photocurrent. Finally, by mixing two cosolvents, we develop a ternary solvent system to tune the fiber width. We propose a model based on nucleation-and-growth which can explain these measurements. Our results show that the width of the semicrystalline polymer fibers is not the result of a frozen dynamical state, but determined by the nucleation induced by the polymer solubility. PMID:26306585

  15. Green polymer chemistry: Synthesis of poly(disulfide) polymers and networks

    NASA Astrophysics Data System (ADS)

    Rosenthal-Kim, Emily Quinn

    The disulfide group is unique in that it presents a covalent bond that is easily formed and cleaved under certain biological conditions. While the ease of disulfide bond cleavage is often harnessed as a method of biodegradation, the ease of disulfide bond formation as a synthetic strategy is often overlooked. The objective this research was to synthesize poly(disulfide) polymers and disulfide crosslinked networks from a green chemistry approach. The intent of the green chemistry approach was to take advantage of the mild conditions applicable to disulfide bond synthesis from thiols. With anticipated use as biomaterials, it was also desired that the polymer materials could be degraded under biological conditions. Here, a new method of poly(disulfide) polymer synthesis is introduced which was inspired by the reaction conditions and reagents found in Nature. Ambient temperatures and aqueous mixtures were used in the new method. Hydrogen peroxide, one of the Nature's most powerful oxidizing species was used as the oxidant in the new polymerization reaction. The dithiol monomer, 3,6-dioxa-1,8-octanedithiol was first solubilized in triethylamine, which activated the thiol groups and made the monomer water soluble. At room temperature, the organic dithiol/amine solution was then mixed with dilute aqueous hydrogen peroxide (3% by weight) to make the poly(disulfide) polymers. The presence of a two phase system (organic and aqueous phases) was critical to the polymerization reaction. As the reaction progresses, a third, polymer phase appeared. At ambient temperatures and above, this phase separated from the reaction mixture and the polymer product was easily removed from the reaction solution. These polymers reach Mn > 250,000 g/mol in under two hours. Molecular weight distributions were between 1.5 and 2.0. Reactions performed in an ice bath which remain below room temperature contain high molecular weight polymers with Mn ≈ 120,000 g/mol and have a molecular weight

  16. Multiphase transport in polymer electrolyte membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Gauthier, Eric D.

    Polymer electrolyte membrane fuel cells (PEMFCs) enable efficient conversion of fuels to electricity. They have enormous potential due to the high energy density of the fuels they utilize (hydrogen or alcohols). Power density is a major limitation to wide-scale introduction of PEMFCs. Power density in hydrogen fuel cells is limited by accumulation of water in what is termed fuel cell `flooding.' Flooding may occur in either the gas diffusion layer (GDL) or within the flow channels of the bipolar plate. These components comprise the electrodes of the fuel cell and balance transport of reactants/products with electrical conductivity. This thesis explores the role of electrode materials in the fuel cell and examines the fundamental connection between material properties and multiphase transport processes. Water is generated at the cathode catalyst layer. As liquid water accumulates it will utilize the largest pores in the GDL to go from the catalyst layer to the flow channels. Water collects to large pores via lateral transport at the interface between the GDL and catalyst layer. We have shown that water may be collected in these large pores from several centimeters away, suggesting that we could engineer the GDL to control flooding with careful placement and distribution of large flow-directing pores. Once liquid water is in the flow channels it forms slugs that block gas flow. The slugs are pushed along the channel by a pressure gradient that is dependent on the material wettability. The permeable nature of the GDL also plays a major role in slug growth and allowing bypass of gas between adjacent channels. Direct methanol fuel cells (DMFCs) have analogous multiphase flow issues where carbon dioxide bubbles accumulate, `blinding' regions of the fuel cell. This problem is fundamentally similar to water management in hydrogen fuel cells but with a gas/liquid phase inversion. Gas bubbles move laterally through the porous GDL and emerge to form large bubbles within the

  17. Computer-Aided Design of Photocured Polymer Networks

    NASA Astrophysics Data System (ADS)

    Sarkar, Swarnavo; Lin-Gibson, Sheng; Chiang, Martin

    Light-initiated free radical polymerization is widely used for manufacturing biomaterials, scaffolds for micomolding, and is being developed as a method for fast 3D fabrication. This process has a large set of control parameters in the composition of the photocurable matrix and the photocuring conditions. But a quantitative map between the choice of parameters and the properties of the resultant polymer is currently unavailable. We present a computational approach to simulate the growth of a polymer network using the stochastic differential equations of reactions and diffusion for a photocuring system. This method allows us to sample trajectories of a growing polymer network in silico. Thus, we provide a computational alternative to synthesize and probe a polymer network for properties like the degree of conversion, structure factor, density of states, and viscosity. We present simulation results that agree with the universal features observed in photopolymerization. Our proposed method enables a thorough and systematic search over the entire parameter space to discover interesting combinations for synthesis.

  18. Activated pathways for the directed insertion of patterned nanoparticles into polymer membranes.

    PubMed

    Ting, Christina L; Frischknecht, Amalie L

    2013-10-28

    We combine the string method with self-consistent field theory to compute the most probable transition pathway, i.e. the minimum free energy path, for the insertion of Janus and protein-like nanoparticles into a polymer membrane bilayer. The method makes no assumptions in the reaction coordinate and overcomes the long timescales challenge associated with simulating rare events. Our study suggests that one approach to building functional polymer–nanoparticle composite membranes with oriented nanoparticles is through electrostatic interactions. In particular, hydrophobic Janus nanoparticles with an asymmetric charge distribution can be made to directionally insert into charged membranes. This process is kinetically driven, and involves overcoming a thermally surmountable activation barrier, which requires favorable interactions between the nanoparticle and the hydrophilic block of the membrane. In contrast, the insertion of protein-like nanoparticles with alternating hydrophilic–hydrophobic–hydrophilic domains into polymer membranes does not occur as a thermally activated event. PMID:26029770

  19. Design and Application of Nanogel-Based Polymer Networks

    NASA Astrophysics Data System (ADS)

    Dailing, Eric Alan

    Crosslinked polymer networks have wide application in biomaterials, from soft hydrogel scaffolds for cell culture and tissue engineering to glassy, high modulus dental restoratives. Composite materials formed with nanogels as a means for tuning network structure on the nanoscale have been reported, but no investigation into nanogels as the primary network component has been explored to this point. This thesis was dedicated to studying network formation from the direct polymerization of nanogels and investigating applications for these unique materials. Covalently crosslinked polymer networks were synthesized from polymerizable nanogels without the use of reactive small monomers or oligomers. Network properties were controlled by the chemical and physical properties of the nanogel, allowing for materials to be designed from nanostructured macromolecular precursors. Nanogels were synthesized from a thermally initiated solution free radical polymerization of a monomethacrylate, a dimethacrylate, and a thiol-based chain transfer agent. Monomers with a range of hydrophilic and hydrophobic character were copolymerized, and polymerizable groups were introduced through an alcohol-isocyanate click reaction. Nanogels were dispersible in water up to 75 wt%, including nanogels that contained a relatively high fraction of a conventionally water-insoluble component. Nanogels with molecular weights that ranged from 10's to 100's of kDa and hydrodynamic radii between 4 and 10 nm were obtained. Macroscopic crosslinked polymer networks were synthesized from the photopolymerization of methacrylate-functionalized nanogels in inert solvent, which was typically water. The nanogel composition and internal branching density affected both covalent and non-covalent interparticle interactions, which dictated the final mechanical properties of the networks. Nanogels with progressively disparate hydrophilic and hydrophobic character were synthesized to explore the potential for creating

  20. Semi-interpenetrating polymer network's of polyimides: Fracture toughness

    NASA Technical Reports Server (NTRS)

    Hansen, Marion Glenn

    1988-01-01

    The objective was to improve the fracture toughness of the PMR-15 thermosetting polyimide by co-disolving LaRC-TPI, a thermoplastic polyimide. The co-solvation of a thermoplastic into a thermoset produces an interpenetration of the thermoplastic polymer into the thermoset polyimide network. A second research program was planned around the concept that to improve the fracture toughness of a thermoset polyimide polymer, the molecular weight between crosslink points would be an important macromolecular topological parameter in producing a fracture toughened semi-IPN polyimide.

  1. High-Performance, Semi-Interpenetrating Polymer Network

    NASA Technical Reports Server (NTRS)

    Pater, Ruth H.; Lowther, Sharon E.; Smith, Janice Y.; Cannon, Michelle S.; Whitehead, Fred M.; Ely, Robert M.

    1992-01-01

    High-performance polymer made by new synthesis in which one or more easy-to-process, but brittle, thermosetting polyimides combined with one or more tough, but difficult-to-process, linear thermoplastics to yield semi-interpenetrating polymer network (semi-IPN) having combination of easy processability and high tolerance to damage. Two commercially available resins combined to form tough, semi-IPN called "LaRC-RP49." Displays improvements in toughness and resistance to microcracking. LaRC-RP49 has potential as high-temperature matrix resin, adhesive, and molding resin. Useful in aerospace, automotive, and electronic industries.

  2. Molecular dynamics in polymers, polymer networks, and model compounds by dielectric relaxation spectroscopy

    NASA Astrophysics Data System (ADS)

    Fitz, Benjamin David

    Segmental dynamics are investigated in model compounds, polymers, and network-forming polymers. Two aspects of these materials are investigated: (1) the role of molecular structure and connectivity on determining the characteristics of the segmental relaxation, and (2) monitoring the variations in the segmental dynamics during network-forming chemical reactions. We quantify the most important aspects of the dynamics: the relaxation shape, the relaxation strength, the relaxation time, and the temperature dependencies of these properties. Additionally, two general segmental dynamics issues of interest are the length-scale and the homogeneous/heterogeneous aspects. A judicious choice of network-forming polymer provides for the determination of an upper bound on the length-scale. A comparison of relaxation characteristics between dynamic light scattering (measuring density fluctuations) and dielectric relaxation spectroscopy (measuring segmental dipolar reorientation) provides one evaluation of the heterogeneity issue. Dipole dynamics in small molecule model compounds show the influence of molecular connectivity on the cooperative molecular response associated with the glass transition. A rigid, nonpolar, cyanate ester network is shown to develop an anomalous relaxation process during crosslinking. A specific local mode of motion is assigned. Additionally, the main relaxation becomes extraordinarily broad during the course of the network formation, due to markedly increased segmental rigidity and loss of configurational entropy.

  3. Electrochemical characterization of electrospun nanocomposite polymer blend electrolyte fibrous membrane for lithium battery.

    PubMed

    Padmaraj, O; Rao, B Nageswara; Venkateswarlu, M; Satyanarayana, N

    2015-04-23

    Novel hybrid (organic/inorganic) electrospun nanocomposite polymer blend electrolyte fibrous membranes with the composition poly(vinylidene difluoride-co-hexafluoropropylene) [P(VdF-co-HFP)]/poly(methyl methacrylate) [P(MMA)]/magnesium aluminate (MgAl2O4)/LiPF6 were prepared by the electrospinning technique. All of the prepared electrospun P(VdF-co-HFP), PMMA blend [90% P(VdF-co-HFP)/10% PMMA], and nanocomposite polymer blend [90% P(VdF-co-HFP)/10% PMMA/x wt % MgAl2O4 (x = 2, 4, 6, and 8)] fibrous membranes were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, differential scanning calorimetry, and scanning electron microscopy. The fibrous nanocomposite separator-cum-polymer blend electrolyte membranes were obtained by soaking the nanocomposite polymer blend membranes in an electrolyte solution containing 1 M LiPF6 in ethylene carbonate (EC)/diethyl carbonate (DEC) (1:1, v/v). The newly developed fibrous nanocomposite polymer blend electrolyte [90% P(VdF-co-HFP)/10% PMMA/6 wt % MgAl2O4/LiPF6] membrane showed a low crystallinity, low average fiber diameter, high thermal stability, high electrolyte uptake, high conductivity (2.60 × 10(-3) S cm(-1)) at room temperature, and good potential stability above 4.5 V. The best properties of the fibrous nanocomposite polymer blend electrolyte (NCPBE) membrane with a 6 wt % MgAl2O4 filler content was used for the fabrication of a Li/NCPBE/LiCoO2 CR 2032 coin cell. The electrochemical performance of the fabricated CR 2032 cell was evaluated at a current density of 0.1 C-rate. The fabricated CR 2032 cell lithium battery using the newly developed NCPBE membrane delivered an initial discharge capacity of 166 mAh g(-1) and a stable cycle performance. PMID:25867205

  4. Swelling behavior of bisensitive interpenetrating polymer networks for microfluidic applications.

    PubMed

    Krause, A T; Zschoche, S; Rohn, M; Hempel, C; Richter, A; Appelhans, D; Voit, B

    2016-07-01

    Bisensitive interpenetrating polymer network (IPN) hydrogels of temperature sensitive net-poly(N-isopropylacrylamide) and pH sensitive net-poly(acrylic acid-co-acrylamide) for microfluidic applications were prepared via a sequential synthesis using free radical polymerization. The IPN indicated a suitable reversible alteration of swelling in response to the change in pH and temperature. The adequate change of the hydrogel volume is a basic requirement for microfluidic applications. Using the introduced correction factor f, it is possible to determine the cooperative diffusion coefficient (Dcoop) of cylindrical samples at any aspect ratio. The determined cooperative diffusion coefficient allowed the evaluation of varying swelling processes of different network structures. The presence of the second sub-network of the IPN improved the swelling behaviour of the first sub-network compared to the individual networks. PMID:27174740

  5. Measurement of water content in polymer electrolyte membranes using high resolution neutron imaging

    SciTech Connect

    Spernjak, Dusan; Mukundan, Rangachary; Borup, Rodney L; Davey, John; Mukherjee, Partha P; Hussey, Daniel S; Jacobson, David

    2010-01-01

    Sufficient water content within a polymer electrolyte membrane (PEM) is necessary for adequate ionic conductivity. Membrane hydration is therefore a fundamental requirement for fuel cell operation. The hydration state of the membrane affects the water transport within, as both the diffusion coefficient and electro-osmotic drag depend on the water content. Membrane's water uptake is conventionally measured ex situ by weighing free-swelling samples equilibrated at controlled water activity. In the present study, water profiles in Nafion{reg_sign} membranes were measured using the high-resolution neutron imaging. The state-of-the-art, 10 {micro}m resolution neutron detector is capable of resolving water distributions across N1120, N1110 and N117 membranes. It provides a means to measure the water uptake and transport properties of fuel cell membranes in situ.

  6. Increased Water Retention in Polymer Electrolyte Membranes at Elevated Temperatures Assisted by Capillary Condensation

    SciTech Connect

    Park, M.J.; Downing, K.H.; Jackson, A.; Gomez, E.D.; Minor, A.M.; Cookson, D.; Weber, A.Z.; Balsara, N.P.

    2008-10-03

    We establish a new systematic methodology for controlling the water retention of polymer electrolyte membranes. Block copolymer membranes comprising hydrophilic phases with widths ranging from 2 to 5 nm become wetter as the temperature of the surrounding air is increased at constant relative humidity. The widths of the moist hydrophilic phases were measured by cryogenic electron microscopy experiments performed on humid membranes. Simple calculations suggest that capillary condensation is important at these length scales. The correlation between moisture content and proton conductivity of the membranes is demonstrated.

  7. Transition from ballistic to electrodiffusive transport in free-standing nanometer-sized polymer membranes

    NASA Astrophysics Data System (ADS)

    Schulze, Susanne; Weitzel, Karl-Michael

    2015-11-01

    The transition from ballistic to electrodiffusive transport of ions through thin polymer membranes has been investigated by recording single transport events via time-correlated single-particle detection. At the highest kinetic energies investigated, ballistic transport of potassium ions is observed with no discernible energy loss to the membrane. At the lowest kinetic energies investigated (several 100 eV) ions are demonstrated to lose the entire kinetic energy to the membrane. Transport there occurs by electrodiffusion. A transition regime is observed. The transition energy is shown to depend on the thickness of the membrane.

  8. Development of NH4+-sensitive polymer membranes for long-term performance microsensors

    NASA Astrophysics Data System (ADS)

    Brzozka, Zbigniew; Dawgul, Marek; Pijanowska, Dorota; Torbicz, Wladislaw

    1997-02-01

    This paper describes the development of NH4+- sensitive membranes based on various polymer materials incorporating nonactine as the ionophore for long-term performance CHEMFETs. Different composition of membranes based on plasticized PVC, carboxylated PVC, plasticized PVC modified by decylmethacrylate, polysiloxane and Siloprene were studied. Although polysiloxane membrane presented the most improved adhesion to the chip surface, the Siloprene membrane was successfully applied to design durable NH4+-sensitive CHEMFETs. These sensors showed NH4+-responses with good selectivity even after 14 months of continuous exposure to conditioning electrolyte.

  9. Novel Elastomeric Membranes Developed for Polymer Electrolytes in Lithium Batteries

    NASA Technical Reports Server (NTRS)

    Tigelaar, Dean M.; Meador, Maryann B.; Kinder, James D.; Bennett, William R.

    2005-01-01

    Lithium-based polymer batteries for aerospace applications need to be highly conductive from -70 to 70 C. State-of-the-art polymer electrolytes are based on polyethylene oxide (PEO) because of the ability of its ether linkages to solvate lithium ions. Unfortunately, PEO has a tendency to form crystalline regions below 60 C, dramatically lowering conductivity below this temperature. PEO has acceptable ionic conductivities (10(exp -4) to 10(exp -3) S/cm) above 60 C, but it is not mechanically strong. The room-temperature conductivity of PEO can be increased by adding solvent or plasticizers, but this comes at the expense of thermal and mechanical stability. One of NASA Glenn Research Center s objectives in the Polymer Rechargeable System program (PERS) is to develop novel polymer electrolytes that are highly conductive at and below room temperature without added solvents or plasticizers.

  10. Dual network model for red blood cell membranes

    NASA Astrophysics Data System (ADS)

    Boal, David H.; Seifert, Udo; Zilker, Andreas

    1992-12-01

    A two-component network is studied by Monte Carlo simulation to model the lipid/spectrin membrane of red blood cells. The model predicts that the shear modulus decreases rapidly with the maximum length of the model spectrin and should be in the 10-7 J/m2 range for human red blood cells. A simplified model for the isolated spectrin network shows a negative Lamé coefficient λ. Transverse fluctuations of the dual membrane are found to be fluidlike over the range of wavelengths investigated.

  11. Shape memory polymer network with thermally distinct elasticity and plasticity

    PubMed Central

    Zhao, Qian; Zou, Weike; Luo, Yingwu; Xie, Tao

    2016-01-01

    Stimuli-responsive materials with sophisticated yet controllable shape-changing behaviors are highly desirable for real-world device applications. Among various shape-changing materials, the elastic nature of shape memory polymers allows fixation of temporary shapes that can recover on demand, whereas polymers with exchangeable bonds can undergo permanent shape change via plasticity. We integrate the elasticity and plasticity into a single polymer network. Rational molecular design allows these two opposite behaviors to be realized at different temperature ranges without any overlap. By exploring the cumulative nature of the plasticity, we demonstrate easy manipulation of highly complex shapes that is otherwise extremely challenging. The dynamic shape-changing behavior paves a new way for fabricating geometrically complex multifunctional devices. PMID:26824077

  12. Dirac Cones in two-dimensional conjugated polymer networks

    NASA Astrophysics Data System (ADS)

    Adjizian, Jean-Joseph; Briddon, Patrick; Humbert, Bernard; Duvail, Jean-Luc; Wagner, Philipp; Adda, Coline; Ewels, Christopher

    2014-12-01

    Linear electronic band dispersion and the associated Dirac physics has to date been limited to special-case materials, notably graphene and the surfaces of three-dimensional (3D) topological insulators. Here we report that it is possible to create two-dimensional fully conjugated polymer networks with corresponding conical valence and conduction bands and linear energy dispersion at the Fermi level. This is possible for a wide range of polymer types and connectors, resulting in a versatile new family of experimentally realisable materials with unique tuneable electronic properties. We demonstrate their stability on substrates and possibilities for doping and Dirac cone distortion. Notably, the cones can be maintained in 3D-layered crystals. Resembling covalent organic frameworks, these materials represent a potentially exciting new field combining the unique Dirac physics of graphene with the structural flexibility and design opportunities of organic-conjugated polymer chemistry.

  13. Enhanced gas separation factors of microporous polymer constrained in the channels of anodic alumina membranes

    PubMed Central

    Chernova, Ekaterina; Petukhov, Dmitrii; Boytsova, Olga; Alentiev, Alexander; Budd, Peter; Yampolskii, Yuri; Eliseev, Andrei

    2016-01-01

    New composite membranes based on porous anodic alumina films and polymer of intrinsic microporosity (PIM-1) have been prepared using a spin-coating technique. According to scanning electron microscopy, partial penetration of polymer into the pores of alumina supports takes place giving rise to selective polymeric layers with fiber-like microstructure. Geometric confinement of rigid PIM-1 in the channels of anodic alumina causes reduction of small-scale mobility in polymeric chains. As a result, transport of permanent gases, such as CH4, becomes significantly hindered across composite membranes. Contrary, the transport of condensable gases (CO2, С4H10), did not significantly suffer from the confinement due to high solubility in the polymer matrix. This strategy enables enhancement of selectivity towards CO2 and C4H10 without significant loss of the membrane performance and seems to be prospective for drain and sweetening of natural gas. PMID:27498607

  14. Enhanced gas separation factors of microporous polymer constrained in the channels of anodic alumina membranes

    NASA Astrophysics Data System (ADS)

    Chernova, Ekaterina; Petukhov, Dmitrii; Boytsova, Olga; Alentiev, Alexander; Budd, Peter; Yampolskii, Yuri; Eliseev, Andrei

    2016-08-01

    New composite membranes based on porous anodic alumina films and polymer of intrinsic microporosity (PIM-1) have been prepared using a spin-coating technique. According to scanning electron microscopy, partial penetration of polymer into the pores of alumina supports takes place giving rise to selective polymeric layers with fiber-like microstructure. Geometric confinement of rigid PIM-1 in the channels of anodic alumina causes reduction of small-scale mobility in polymeric chains. As a result, transport of permanent gases, such as CH4, becomes significantly hindered across composite membranes. Contrary, the transport of condensable gases (CO2, С4H10), did not significantly suffer from the confinement due to high solubility in the polymer matrix. This strategy enables enhancement of selectivity towards CO2 and C4H10 without significant loss of the membrane performance and seems to be prospective for drain and sweetening of natural gas.

  15. Interactive Thermal Effects on Metal-Organic Framework Polymer Composite Membranes.

    PubMed

    Cacho-Bailo, Fernando; Téllez, Carlos; Coronas, Joaquín

    2016-07-01

    Polymeric membranes are important tools for intensifying separation processes in chemical industries, concerning strategic tasks such as CO2 sequestration, H2 production, and water supply and disposal. Mixed-matrix and supported membranes have been widely developed; recently many of them have been based on metal-organic frameworks (MOFs). However, most of the impacts MOFs have within the polymer matrix have yet to be determined. The effects related to thermal behavior arising from the combination of MOF ZIF-8 and polysulfone have now been quantified. The catalyzed oxidation of the polymer is strongly affected by the MOF crystal size and distribution inside the membrane. A 16 wt % 140 nm-sized ZIF-8 loading causes a 40 % decrease in the observed activation energy of the polysulfone oxidation that takes place at a temperature (545 °C) 80 °C lower than in the raw polymer (625 °C). PMID:27156113

  16. Three-dimensional conformal coatings through the entrapment of polymer membrane precursors.

    PubMed

    Nguyen, Du T; Kleiman, Maya; Ryu, Keun Ah; Hiew, Stanley; Brubaker, Kyle; Mughnetsyan, Rafik; Truong, Richard; Dolan, Benjamin; Tackett, Edward; Esser-Kahn, Aaron P

    2014-02-26

    We report a technique to coat polymers onto 3D surfaces distinct from traditional spray, spin, or dip coating. In our technique, the surface of a template structure composed of poly(lactic acid) swells and entraps a soluble polymer precursor. Once entrapped, the precursor is cured, resulting in a thin, conformal membrane. The thickness of each coating depends on the coating solution composition, residence time, and template size. Thicknesses ranged from 400 nm to 4 μm within the experimental conditions we explored. The coating method was compatible with a range of polymers. Complicated 3D structures and microstructures of 10 μm thickness and separation were coated using this technique. The templates can also be selectively removed, leaving behind a hollow membrane structure in the shape of the original printed, extruded, or microporous template structures. This technique may be useful in applications that benefit from three-dimensional membrane topologies, including catalysis, separations, and potentially tissue engineering. PMID:24437474

  17. Enhanced gas separation factors of microporous polymer constrained in the channels of anodic alumina membranes.

    PubMed

    Chernova, Ekaterina; Petukhov, Dmitrii; Boytsova, Olga; Alentiev, Alexander; Budd, Peter; Yampolskii, Yuri; Eliseev, Andrei

    2016-01-01

    New composite membranes based on porous anodic alumina films and polymer of intrinsic microporosity (PIM-1) have been prepared using a spin-coating technique. According to scanning electron microscopy, partial penetration of polymer into the pores of alumina supports takes place giving rise to selective polymeric layers with fiber-like microstructure. Geometric confinement of rigid PIM-1 in the channels of anodic alumina causes reduction of small-scale mobility in polymeric chains. As a result, transport of permanent gases, such as CH4, becomes significantly hindered across composite membranes. Contrary, the transport of condensable gases (CO2, С4H10), did not significantly suffer from the confinement due to high solubility in the polymer matrix. This strategy enables enhancement of selectivity towards CO2 and C4H10 without significant loss of the membrane performance and seems to be prospective for drain and sweetening of natural gas. PMID:27498607

  18. Millimeter thick ionic polymer membrane-based IPMCs with bimetallic Pd-Pt electrodes

    NASA Astrophysics Data System (ADS)

    Palmre, Viljar; Kim, Sung Jun; Kim, Kwang

    2011-04-01

    Ionic polymer metal composites (IPMC) are a low-voltage driven Electroactive Polymers (EAP) that can be used as actuators or sensors. This paper presents a comparative study of millimeter thick ionic polymer membrane-based IPMCs with high-performance Pd-Pt electrodes and conventional Pt electrodes. IPMCs assembled with different electrodes are characterized in terms of electromechanical, -chemical and mechanolelectrical properties. The SEM and energy dispersive X-ray (EDS) analysis are used to investigate the distribution of deposited electrode metals in the cross-section of Pd-Pt IPMCs. The study shows that IPMCs assembled with millimeter thick ionic polymer membranes and bimetallic Pd-Pt electrodes are superior in mechanoelectrical sensing and, also, show considerably higher blocking forces compared to the conventional type of IPMCs. Blocking forces more than 30 grams are measured under 4V DC. However, the actuation response is slower than conventional IPMCs having approximately 0.2-0.3 mm thickness.

  19. TEST AND EVALUATION OF A POLYMER MEMBRANE PRECONCENTRATOR

    EPA Science Inventory

    The report gives results of an evaluation of the applicability of membrane systems as a preconcentrator and defines operating parameters of a membrane system. Advantages of such a system is a potential reduction in cost for subsequent control systems. The evaluation is part of a ...

  20. High performance radiation-grafted membranes and electrodes for polymer electrolyte fuel cells

    SciTech Connect

    Nezu, Shinji; Seko, Hideo; Gondo, Masaki; Ito, Naoki

    1996-12-31

    Polymer electrolyte fuel cells (PEFC) have attracted much attention for stationary and electric vehicle applications. Much progress has been made to improve their performance recently. However there are still several problems to overcome for commercialization. Among them, the cost of polymer electrolyte membranes seems to be rather critical, because a cost estimate of a practical fuel cell stack shows that the membrane cost must be reduced at least by two orders of magnitude based on current perfluorosulfonic acid membranes eg. Nafion{reg_sign}. Thus the development of new membrane materials is strongly desired. Styrene grafted tetrafluoroethylene-hexafluoropropylene copolymer (FEP) membranes have been studied for a fuel cell application by G. Scherer et al. These authors showed that membranes obtained by radiation grafting served as an alternative membrane for fuel cells although there were several problems to overcome in the future. These problems include shorter life time which was concluded to result from the decomposition of grafted polystyrene side chains. We report here the performance of our fuel cells which were fabricated from our radiation grafted membranes (IMRA MEMBRANE) and gas diffusion electrodes.

  1. Flash freezing route to mesoporous polymer nanofibre networks

    PubMed Central

    Samitsu, Sadaki; Zhang, Rui; Peng, Xinsheng; Krishnan, Mohan Raj; Fujii, Yoshihisa; Ichinose, Izumi

    2013-01-01

    There are increasing requirements worldwide for advanced separation materials with applications in environmental protection processes. Various mesoporous polymeric materials have been developed and they are considered as potential candidates. It is still challenging, however, to develop economically viable and durable separation materials from low-cost, mass-produced materials. Here we report the fabrication of a nanofibrous network structure from common polymers, based on a microphase separation technique from frozen polymer solutions. The resulting polymer nanofibre networks exhibit large free surface areas, exceeding 300 m2 g−1, as well as small pore radii as low as 1.9 nm. These mesoporous polymer materials are able to rapidly adsorb and desorb a large amount of carbon dioxide and are also capable of condensing organic vapours. Furthermore, the nanofibres made of engineering plastics with high glass transition temperatures over 200 °C exhibit surprisingly high, temperature-dependent adsorption of organic solvents from aqueous solution. PMID:24145702

  2. Reconfigurable Polymer Networks for Improved Treatment of Intracranial Aneurysms

    NASA Astrophysics Data System (ADS)

    Ninh, Chi Suze Q.

    Endovascular embolization of intracranial aneurysms is a minimally invasive treatment in which an implanted material forms a clot to isolate the weakened vessel. Current strategy suffers from long-term potential failure modes. These potential failure modes include (1) enzymatic degradation of the fibrin clot that leads to compaction of the embolic agent, (2) incomplete filling of the aneurysm sac by embolic agent, and (3) challenging geometry of wide neck aneurysms. In the case of wide neck aneurysms, usually an assisting metal stent is used to help open the artery. However, metal stents with much higher modulus in comparison to the soft blood vessel can cause biocompatibilities issues in the long term such as infection and scarring. Motivated to solve these challenges associated with endovascular embolization, strategies to synthesize and engineer reconfigurable and biodegradable polymers as alternative therapies are evaluated in this thesis. (1) Reconfiguration of fibrin gel's modulus was achieved through crosslinking with genipin released from a biodegradable polymer matrix. (2) Reconfigurability can also be achieved by transforming triblock co-polymer hydrogel into photoresponsive material through incorporation of melanin nanoparticles as efficient photosensitizers. (3) Finally, reconfigurability can be conferred on biodegradable polyester networks via Diels-Alder coupling of furan pendant groups and dimaleimide crosslinking agent. Taken all together, this thesis describes strategies to transform a broad class of polymer networks into reconfigurable materials for improved treatment of intracranial aneurysms as well as for other biomedical applications.

  3. Shape memory polymers based on uniform aliphatic urethane networks

    SciTech Connect

    Wilson, T S; Bearinger, J P; Herberg, J L; Marion III, J E; Wright, W J; Evans, C L; Maitland, D J

    2007-01-19

    Aliphatic urethane polymers have been synthesized and characterized, using monomers with high molecular symmetry, in order to form amorphous networks with very uniform supermolecular structures which can be used as photo-thermally actuable shape memory polymers (SMPs). The monomers used include hexamethylene diisocyanate (HDI), trimethylhexamethylenediamine (TMHDI), N,N,N{prime},N{prime}-tetrakis(hydroxypropyl)ethylenediamine (HPED), triethanolamine (TEA), and 1,3-butanediol (BD). The new polymers were characterized by solvent extraction, NMR, XPS, UV/VIS, DSC, DMTA, and tensile testing. The resulting polymers were found to be single phase amorphous networks with very high gel fraction, excellent optical clarity, and extremely sharp single glass transitions in the range of 34 to 153 C. Thermomechanical testing of these materials confirms their excellent shape memory behavior, high recovery force, and low mechanical hysteresis (especially on multiple cycles), effectively behaving as ideal elastomers above T{sub g}. We believe these materials represent a new and potentially important class of SMPs, and should be especially useful in applications such as biomedical microdevices.

  4. Nanoparticle networks reduce the flammability of polymer nanocomposites

    NASA Astrophysics Data System (ADS)

    Kashiwagi, Takashi; Du, Fangming; Douglas, Jack F.; Winey, Karen I.; Harris, Richard H.; Shields, John R.

    2005-12-01

    Synthetic polymeric materials are rapidly replacing more traditional inorganic materials, such as metals, and natural polymeric materials, such as wood. As these synthetic materials are flammable, they require modifications to decrease their flammability through the addition of flame-retardant compounds. Environmental regulation has restricted the use of some halogenated flame-retardant additives, initiating a search for alternative flame-retardant additives. Nanoparticle fillers are highly attractive for this purpose, because they can simultaneously improve both the physical and flammability properties of the polymer nanocomposite. We show that carbon nanotubes can surpass nanoclays as effective flame-retardant additives if they form a jammed network structure in the polymer matrix, such that the material as a whole behaves rheologically like a gel. We find this kind of network formation for a variety of highly extended carbon-based nanoparticles: single- and multiwalled nanotubes, as well as carbon nanofibres.

  5. Gluconic acid production in bioreactor with immobilized glucose oxidase plus catalase on polymer membrane adjacent to anion-exchange membrane.

    PubMed

    Godjevargova, Tzonka; Dayal, Rajeshwar; Turmanova, Sevdalina

    2004-10-20

    Gluconic acid was obtained in the permeate side of the bioreactor with glucose oxidase (GOD) immobilized onto anion-exchange membrane (AEM) of low-density polyethylene grafted with 4-vinylpiridine. The electric resistance of the anion-exchange membranes was increased after the enzyme immobilization on the membrane. The gluconic acid productions were relatively low with the GOD immobilized by any method on the AEM. To increase the enzyme reaction efficiency, GOD was immobilized on membrane of AN copolymer (PAN) adjacent to an anion-exchange membrane in bioreactor. Uses of anion-exchange membrane led to selective removal of the gluconic acid from the glucose solution and reduce the gluconic acid inhibition. The amount of gluconic acid obtained in the permeate side of the bioreactor with the GOD immobilized on the PAN membrane adjacent to the AEM under electrodialysis was about 30 times higher than that obtained with enzyme directly bound to the AEM. The optimal substrate concentration in the feed side was found to be about 1 g/l. Further experiments were carried out with the co-immobilized GOD plus Catalase (CAT) on the PAN membrane adjacent to the AEM to improve the efficiency of the immobilize system. The yield of this process was at least 95%. The storage stability of the co-immobilized GOD and CAT was studied (lost 20% of initial activity for 90 d). The results obtained clearly showed the higher potential of the dual membrane bioreactor with GOD plus CAT bound to ultrafiltration polymer membrane adjacent to the AEM. Storage stability of GOD activity in GOD plus CAT immobilized on PAN//AEM membranes and on AEM. PMID:15497133

  6. Modeling the effect of nano-sized polymer particles on the properties of lipid membranes

    NASA Astrophysics Data System (ADS)

    Rossi, Giulia; Monticelli, Luca

    2014-12-01

    The interaction between polymers and biological membranes has recently gained significant interest in several research areas. On the biomedical side, dendrimers, linear polyelectrolytes, and neutral copolymers find application as drug and gene delivery agents, as biocidal agents, and as platforms for biological sensors. On the environmental side, plastic debris is often disposed of in the oceans and gets degraded into small particles; therefore concern is raising about the interaction of small plastic particles with living organisms. From both perspectives, it is crucial to understand the processes driving the interaction between polymers and cell membranes. In recent times progress in computer technology and simulation methods has allowed computational predictions on the molecular mechanism of interaction between polymeric materials and lipid membranes. Here we review the computational studies on the interaction between lipid membranes and different classes of polymers: dendrimers, linear charged polymers, polyethylene glycol (PEG) and its derivatives, polystyrene, and some generic models of polymer chains. We conclude by discussing some of the technical challenges in this area and future developments.

  7. Interpenetrating Polymer Networks as Innovative Drug Delivery Systems

    PubMed Central

    Lohani, Alka; Singh, Garima; Bhattacharya, Shiv Sankar; Verma, Anurag

    2014-01-01

    Polymers have always been valuable excipients in conventional dosage forms, also have shown excellent performance into the parenteral arena, and are now capable of offering advanced and sophisticated functions such as controlled drug release and drug targeting. Advances in polymer science have led to the development of several novel drug delivery systems. Interpenetrating polymer networks (IPNs) have shown superior performances over the conventional individual polymers and, consequently, the ranges of applications have grown rapidly for such class of materials. The advanced properties of IPNs like swelling capacity, stability, biocompatibility, nontoxicity and biodegradability have attracted considerable attention in pharmaceutical field especially in delivering bioactive molecules to the target site. In the past few years various research reports on the IPN based delivery systems showed that these carriers have emerged as a novel carrier in controlled drug delivery. The present review encompasses IPNs, their types, method of synthesis, factors which affects the morphology of IPNs, extensively studied IPN based drug delivery systems, and some natural polymers widely used for IPNs. PMID:24949205

  8. A computational molecular design framework for crosslinked polymer networks.

    PubMed

    Eslick, J C; Ye, Q; Park, J; Topp, E M; Spencer, P; Camarda, K V

    2009-05-21

    Crosslinked polymers are important in a very wide range of applications including dental restorative materials. However, currently used polymeric materials experience limited durability in the clinical oral environment. Researchers in the dental polymer field have generally used a time-consuming experimental trial-and-error approach to the design of new materials. The application of computational molecular design (CMD) to crosslinked polymer networks has the potential to facilitate development of improved polymethacrylate dental materials. CMD uses quantitative structure property relations (QSPRs) and optimization techniques to design molecules possessing desired properties. This paper describes a mathematical framework which provides tools necessary for the application of CMD to crosslinked polymer systems. The novel parts of the system include the data structures used, which allow for simple calculation of structural descriptors, and the formulation of the optimization problem. A heuristic optimization method, Tabu Search, is used to determine candidate monomers. Use of a heuristic optimization algorithm makes the system more independent of the types of QSPRs used, and more efficient when applied to combinatorial problems. A software package has been created which provides polymer researchers access to the design framework. A complete example of the methodology is provided for polymethacrylate dental materials. PMID:23904665

  9. Microstructure and rheology of microfibril-polymer networks.

    PubMed

    Veen, Sandra J; Versluis, Peter; Kuijk, Anke; Velikov, Krassimir P

    2015-12-14

    By using an adsorbing polymer in combination with mechanical de-agglomeration, the microstructure and rheological properties of networks of microfibrils could be controlled. By the addition of sodium carboxymethyl cellulose during de-agglomeration of networks of bacterial cellulose, the microstructure could be changed from an inhomogeneous network with bundles of microfibrils and voids to a more homogeneous spread and alignment of the particles. As a result the macroscopic rheological properties were altered. Although still elastic and gel-like in nature, the elasticity and viscous behavior of the network as a function of microfibril concentration is altered. The microstructure is thus changed by changing the surface properties of the building blocks leading to a direct influence on the materials macroscopic behavior. PMID:26434637

  10. Nanostructural surface engineering of grafted polymers on inorganic oxide substrates for membrane separations

    NASA Astrophysics Data System (ADS)

    Yoshida, Wayne Hiroshi

    Nanostructural engineering of inorganic substrates by free radical graft polymerization was studied with the goal of developing new membrane materials for pervaporation. Graft polymerization consisted of modification of surface hydroxyls with vinyl trimethoxysilane, followed by solution graft polymerization reaction using either vinyl acetate (VAc) or vinyl pyrrolidone (VP). The topology of the modified surfaces was studied by atomic force microscopy (AFM) on both atomically smooth silicon wafer substrates and microporous inorganic membrane supports in order to deduce the effects of modification on the nanostructural properties of the membrane. While unmodified wafers showed a root-mean-square (RMS) surface roughness of 0.21 +/- 0.03 nm, roughness increased to 3.15 +/- 0.23 nm upon silylation. Under poor solvent conditions (i.e., air), surfaces modified with higher poly(vinyl acetate) (PVAc) or poly(vinyl pyrrolidone) (PVP) polymer graft yields displayed lateral inhomogeneities in the polymer layer. Although RMS surface roughness was nearly identical (0.81--0.85 nm) for PVAc-modified surfaces grafted at different monomer concentrations, the skewness of the height distribution decreased from 2.22 to 0.78 as polymer graft yield increased from 0.8 to 3.5 mg/m2. The polymer-modified surfaces were used to create inorganic pervaporation membranes consisting of a single macromolecular separation layer formed by graft polymerization. PVAc grafted silica membranes (500A native pore size) were found selective for MTBE in the separation of 0.1--1% (v/v) MTBE from water, achieving MTBE enrichment factors as high as 371 at a permeate flux of 0.38 l/m2 hr and a Reynolds number of 6390; however, these membranes could not separate anhydrous organic mixtures. Pervaporative separation of methanol/MTBE mixtures was possible with PVAc and PVP-modified alumina supports of 50A native pore size, where the separation layer consisted of grafted polymer chains with estimated radius of